JP2008133467A - Method for manufacturing rigid foam synthetic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a rigid foam excellent in the reactivity and execution nature that can meet the spray method with little use of a metallic catalyst, such as a lead compound, that may cause environmental problems, and without a sharply increased amount of an amine catalyst. <P>SOLUTION: The method of manufacturing the rigid foam synthetic resin uses a polyol which comprises the following polyol (A) and polyol (B) and in which the proportion of ethylene oxide occupying in the total alkylene oxides to be subjected to the ring-opening addition polymerization is 30-60 mass%. Here, the polyol (A) is a polyether polyol prepared by the ring-opening addition polymerization of alkylene oxides to an aliphatic and/or alicyclic amine and having a hydroxyl value of 100-800 mgKOH/g and a proportion of ethylene oxide of ≥25 mass%, and the polyol (B) is a polyether polyol prepared by the ring-opening addition polymerization of alkylene oxides to a Mannich condensation product and having a hydroxyl value of 200-500 mgKOH/g. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a rigid foamed synthetic resin such as rigid polyurethane foam. In particular, the present invention relates to a method for producing a rigid foam synthetic resin suitable for a construction method that requires a quick reaction such as a spray method.

  A polyol and a polyisocyanate are reacted and foamed in the presence of a foam stabilizer, a catalyst and a foaming agent to produce a rigid foamed synthetic resin (hereinafter collectively referred to as a rigid foam) such as a rigid polyurethane foam and a rigid polyisocyanurate foam. Manufacturing is widely done. Since the rigid foam has a high degree of freedom in molding and is excellent in heat insulating performance, it is suitably used as a heat insulating material for various devices or buildings.

Of these, in the case of constructing a heat insulating material for a building that is particularly large in a refrigerated warehouse and requires high heat insulation performance, construction of a hard foam by a spray method is often employed. Here, the spray method is a method in which a raw material is fed at a high pressure, a raw material liquid is sprayed from a spray gun onto a wall surface or the like to be constructed, and foamed on the wall surface or the like to form a heat insulating material or the like.
The advantage of the spray method is that a heat insulating material having a desired thickness can be constructed regardless of the shape of the wall surface or the like that is the object of construction. Among spraying methods, the multilayer spraying method can laminate a rigid foam in multiple layers to form a thick heat insulating layer having high heat insulating performance.
In this spray method, the reaction liquid sprayed on the wall surface or the like needs to be quickly foamed and cured. For this reason, it is common to use a metal catalyst such as a lead compound having a high catalytic activity.

However, in recent years, from the viewpoint of accumulation and harmfulness to the human body, strict management is required regarding the discharge and disposal of lead compounds and the like. Even in the above spray method, although the amount of catalyst used is very small, it is desired to perform the construction without using a lead compound catalyst or the like.
Therefore, a technology is disclosed in which a specific amine catalyst is used and a certain amount of a hydroxyalkylated polyalkylene polyamine is added to increase the reactivity at the time of producing a rigid foam without using a lead compound catalyst (patent) Reference 1).
In addition, in the water foam spray method, a technique for compensating for reactivity by using a bismuth compound or the like as a catalyst is disclosed (see Patent Documents 2 and 3). Moreover, the method of improving reaction activity by using together a piperazine-type polyol is disclosed (patent documents 4-6).
JP 2006-233044 A JP 2005-307147 A JP 2005-307144 A JP-A-7-149867 JP-A-8-100044 JP 2005-206819 A

However, in patent document 1, the manufacture evaluation of the rigid foam by a spray method is not performed. In addition, the bismuth compound used in Patent Documents 2 and 3 has a lower catalytic activity than the lead compound. Therefore, it is necessary to relatively increase the amount of the amine catalyst to be combined, which causes problems in the working environment such as odor and eye rainbow. May occur. On the other hand, the present inventors have conducted various studies so far, such as improvement of reaction activity by using a piperazine-based polyol in combination (see Patent Documents 4, 5, and 6) and development of a new Mannich polyol (Patent Document 3). I have done it. However, the reaction activity and the construction method in the case of not using any lead compound have not been studied.
The present invention solves the above problems, uses no or almost no metal catalyst that may cause environmental problems such as lead compounds, and can be used in a spray method without significantly increasing the amount of amine catalyst. It is an object of the present invention to provide a method for producing a rigid foam which has reactivity and is excellent in enforceability by a spray method.

The present invention employs the following configuration.
[1] In a method for producing a rigid foam synthetic resin by reacting a polyol and a polyisocyanate in the presence of a foaming agent, a foam stabilizer and a catalyst, the polyol contains the following polyol (A) and polyol (B): A method for producing a rigid foam synthetic resin, wherein the proportion of ethylene oxide in the total alkylene oxide to be subjected to ring-opening addition polymerization is 30 to 60% by mass.
Polyol (A): Polyether polyol having a hydroxyl value of 100 to 800 mgKOH / g obtained by ring-opening addition polymerization of alkylene oxide to initiator (S1). Initiator (S1) is composed of aliphatic amine and fat A polyether polyol which is at least one selected from the group consisting of cyclic amines, and the proportion of ethylene oxide in the alkylene oxide to be subjected to ring-opening addition polymerization is 25% by mass or more.
Polyol (B): a polyether polyol having a hydroxyl value of 200 to 500 mgKOH / g obtained by ring-opening addition polymerization of alkylene oxide to initiator (S2). Initiator (S2) is phenols or aldehydes. And a polyether polyol which is a Mannich condensation product obtained by reacting alkanolamines.

[2] The hard material according to [1], wherein the polyol (A) includes a polyol (A1) having a hydroxyl value of 100 to 700 mgKOH / g obtained by ring-opening addition polymerization of ethylene oxide to the initiator (S1). A method for producing foamed synthetic resin.
[3] The polyol (A) contains a polyol (A2) having a hydroxyl value of 250 to 800 mgKOH / g obtained by ring-opening addition polymerization of propylene oxide to the initiator (S1) [1] or [2 ] The manufacturing method of the hard foaming synthetic resin of description.
[4] The method for producing a rigid foam synthetic resin according to any one of [1] to [3], wherein the initiator (S1) is ethylenediamine and / or piperazine.
[5] The method for producing a rigid foam synthetic resin according to any one of [1] to [4], wherein the polyol (B) has a ratio of ethylene oxide to alkylene oxide to be subjected to ring-opening addition polymerization of 50 to 95% by mass. .
[6] The method for producing a rigid foam synthetic resin according to any one of [1] to [5], wherein the polyol contains 20 to 80% by mass of the polyol (A) and 5 to 40% by mass of the polyol (B).
[7] The polyol further includes a polyol (C) obtained by ring-opening addition polymerization of an alkylene oxide to a polyhydric alcohol and having a hydroxyl number of 2 to 4 and a hydroxyl value of 25 to 200 mg KOH / g. [1] The method for producing a rigid foamed synthetic resin according to any one of [6].

[8] The method for producing a rigid foam synthetic resin according to any one of [1] to [7], wherein the catalyst comprises a compound of a metal other than lead, tin, and mercury, and a tertiary amine.
[9] The method for producing a hard foam synthetic resin according to any one of claims 1 to 8, which is performed by a spray method.
[10] The method for producing a rigid foam synthetic resin according to [9], wherein the spray method is a multilayer spray method.

  According to the method for producing a rigid foam synthetic resin of the present invention, no or little metal catalyst that may cause environmental problems such as lead compounds is used, and the amount of amine catalyst is not greatly increased. High reactivity can be obtained. Moreover, according to the manufacturing method of the hard foam synthetic resin of this invention, the outstanding workability is obtained in the spray method, especially the multilayer spraying method.

  In the method for producing a rigid foam of the present invention, a specific polyol and a polyisocyanate compound are reacted in the presence of a foaming agent, a foam stabilizer and a catalyst to produce a rigid foamed synthetic resin. The details will be described below.

[Polyol]
The polyol in the present invention includes the following polyol (A) and polyol (B), and the proportion of ethylene oxide in the total alkylene oxide to be subjected to ring-opening addition polymerization is 30 to 60% by mass, preferably 30 to 55% by mass. Use things. When the ratio of ethylene oxide is within the above range, the reactivity with polyisocyanate is increased, and the adhesiveness of the resulting rigid foam is improved.

  The hydroxyl value of the whole polyol of the present invention is preferably 300 to 600 mgKOH / g, more preferably 300 to 550 mgKOH / g. If the said hydroxyl value is this range, since the rigid foam of a favorable physical property is obtained with a spray method, it is preferable.

(Polyol (A))
The polyol (A) is a polyether polyol having a hydroxyl value of 100 to 800 mgKOH / g obtained by ring-opening addition polymerization of an alkylene oxide to the initiator (S1). The initiator (S1) is an aliphatic amine and It is a polyether polyol which is at least one selected from the group consisting of alicyclic amines and has a proportion of ethylene oxide in the alkylene oxide to be subjected to ring-opening addition polymerization of 25% by mass or more.

The initiator (S1) is at least one selected from the group consisting of aliphatic amines and alicyclic amines.
Examples of the aliphatic amine include alkylamines and alkanolamines. Examples of alkyl amines include ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, and triethylene tetraamine. Examples of the alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, aminoethylethanolamine and the like.

Examples of alicyclic amines include piperidines, piperazines, and pyrrolidines.
Examples of piperidines include 1- (2-aminoethyl) piperidine. Examples of piperazines include piperazine, N-aminomethylpiperazine, 1- (2-aminoethyl) piperazine and the like. Examples of pyrrolidines include 1- (2-aminoethyl) pyrrolidine.

In the polyol (A), the proportion of ethylene oxide in the alkylene oxide to be subjected to ring-opening addition polymerization to the initiator (S1) is 25% by mass or more, preferably 25 to 70% by mass, and preferably 25 to 65% by mass. It is more preferable.
Propylene oxide is preferably used as the alkylene oxide other than ethylene oxide.
When the ratio of ethylene oxide increases, the ratio of primary hydroxyl groups present in the polyol (A) increases and the reactivity of the polyol (A) increases. Moreover, the adhesiveness of the rigid foam obtained improves.

The hydroxyl value of the polyol (A) is 100 to 800 mgKOH / g, and preferably 250 to 800 mgKOH / g.
When the hydroxyl value is 100 mgKOH / g or more, the resulting rigid foam is difficult to shrink. When the hydroxyl value is 800 mgKOH / g or less, mechanical properties can be imparted to the resulting rigid foam while the viscosity of the polyol is kept low.

  The polyol (A) is preferably 20 to 80% by mass, more preferably 35 to 80% by mass, and still more preferably 40 to 80% by mass of the entire polyol. When the ratio of the polyol (A) is within this range, the activity of the polyol becomes sufficiently high, and the appearance of the foam can be kept good. Moreover, it is effective in improving the adhesiveness of the obtained rigid foam.

(Polyol (A1))
The polyol (A) preferably contains a polyol (A1) having a hydroxyl value of 100 to 700 mgKOH / g obtained by ring-opening addition polymerization of ethylene oxide to the initiator (S1).
By including the polyol (A1), the reactivity of the polyol (A) is increased. Moreover, the adhesiveness of the rigid foam obtained improves.

  In the polyol (A1), an alicyclic amine is preferably used as the initiator (S1), piperazines are more preferably used, and piperazine substituted with an aminoalkyl group is most preferably used. Piperazine has a high effect as a catalyst for promoting the urethane bond formation reaction, and by using it as an initiator of the polyol (A1), an effect of increasing the reactivity at the time of producing the rigid foam can be obtained.

  In the polyol (A1), all alkylene oxides to be subjected to ring-opening addition polymerization to the initiator (S1) are ethylene oxide. By using only ethylene oxide, the hydroxyl groups of the polyol (A1) are all primary hydroxyl groups, and the reactivity of the polyol (A1) is increased. Moreover, the adhesiveness of the rigid foam obtained improves.

The hydroxyl value of the polyol (A1) is 100 to 700 mgKOH / g, and preferably 250 to 700 mgKOH / g. When the hydroxyl value of the polyol (A1) is within the above range, the reactivity of the polyol compound can be increased, and the adhesiveness of the rigid foam can be easily secured, which is preferable. A polyol (A1) may be used individually by 1 type, and may use 2 or more types together. When two or more polyols are used in combination as the polyol (A1), the average hydroxyl value after combining the respective polyols only needs to satisfy the above range.
2-8 are preferable and, as for the average functional group number of a polyol (A1), 2-6 are more preferable. The average number of functional groups of the polyol (A1) is equal to the number average of active hydrogen atoms of the initiator (S1) used for the production of the polyol (A1).

  The polyol (A1) is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and still more preferably 20 to 50% by mass based on the total polyol. When the proportion of the polyol (A1) is 10% by mass or more, sufficiently high reactivity can be obtained without using a metal catalyst that may cause environmental problems such as lead compounds as a catalyst. Moreover, the adhesiveness of the rigid foam obtained becomes favorable. Moreover, if the ratio of a polyol (A1) is 60 mass% or less, it is preferable that the obtained rigid foam tends to be sufficient strength.

(Polyol (A2))
The polyol (A) preferably contains a polyol (A2) having a hydroxyl value of 250 to 800 mgKOH / g obtained by ring-opening addition polymerization of propylene oxide to the initiator (S1).
By including the polyol (A2), it is possible to keep the vapor pressure of the whole raw material low even when HFC is used as the foaming agent. Moreover, when it constructs by the spray method, the lateral flow of foam can be suppressed.

  In the polyol (A2), it is preferable to use an aliphatic amine as the initiator (S1), more preferably an alkylamine, and most preferably ethylenediamine.

  In the polyol (A2), all of the alkylene oxide to be subjected to ring-opening addition polymerization to the initiator (S1) is propylene oxide. By using only propylene oxide, the vapor pressure of the entire raw material can be kept low even when HFC is used as the blowing agent.

The hydroxyl value of the polyol (A2) is 250 to 800 mgKOH / g, and preferably 280 to 770 mgKOH / g. When the hydroxyl value of the polyol (A2) is within the above range, the resulting rigid foam has good mechanical strength and the like. Moreover, even when HFC is used as the foaming agent, the vapor pressure of the entire raw material can be kept low.
2-8 are preferable and, as for the average functional group number of a polyol (A2), 2-6 are more preferable. The average number of functional groups of the polyol (A2) is equal to the number average of active hydrogen atoms of the initiator (S1) used for the production of the polyol (A2).

  The polyol (A2) is preferably 0 to 50% by mass, more preferably 20 to 50% by mass, based on the entire polyol. Within this range, characteristics such as mechanical strength of the resulting rigid foam can be exhibited, and even when an HFC compound is used as a foaming agent, the vapor pressure of the raw material system can be kept low.

(Polyol (A3))
The polyol (A) may contain a polyol (A3) other than the polyol (A1) or (A2).
The proportion of the polyol (A3) is preferably 50% by mass or less, more preferably 45% by mass or less of the entire polyol.
In the polyol (A3), it is preferable to use ethylene oxide and propylene oxide in combination as the alkylene oxide to be subjected to ring-opening addition polymerization to the initiator (S1). In this case, the order of ring-opening addition polymerization is preferably propylene oxide first and ethylene oxide later.

(Polyol (B))
Polyol (B) is a polyether polyol having a hydroxyl value of 200 to 500 mgKOH / g obtained by ring-opening addition polymerization of alkylene oxide to initiator (S2). Initiator (S2) is a phenol, aldehyde And a polyether polyol which is a Mannich condensation product obtained by reacting alkanolamines.

Here, examples of phenols include phenol, nonylphenol, cresol, bisphenol A, resorcinol and the like. Among these, nonylphenol is preferable in terms of improving the compatibility between the polyol and the polyisocyanate and improving the cell appearance.
Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde and the like, and formaldehyde and paraformaldehyde are preferable in terms of improving the adhesiveness of the foam.
Examples of alkanolamines include monoethanolamine, diethanolamine, 1-amino-2-propanol, and aminoethylethanolamine. Of these, diethanolamine is preferred for balancing the improvement in strength of the resulting rigid foam and the reduction in the viscosity of the polyol.

It is preferable that the ratio of the raw material at the time of obtaining an initiator (S2) is 1-3 mol of aldehydes, and 2-3 mol of alkanolamines with respect to 1 mol of phenols. If it is this range, generation | occurrence | production of the odor at the time of manufacturing a rigid foam is suppressed, a viscosity is suppressed low, and the adhesiveness of the rigid foam obtained tends to become favorable, etc. are preferable.
In the ratio of the raw materials, the ratio of aldehydes to 1 mol of phenols is more preferably 1.2 to 2.5 mol, and further preferably 1.4 to 2.3 mol. Similarly, the ratio of alkanolamines to 1 mol of phenols is more preferably 1.2 to 2.5 mol, and further preferably 1.4 to 2.3 mol.

In the polyol (B), the proportion of ethylene oxide in the alkylene oxide to be subjected to ring-opening addition polymerization to the initiator (S2) is preferably 20 to 95% by mass, more preferably 35 to 85% by mass, More preferably, it is -80 mass%.
By setting this ratio, the compatibility between the polyol (B) and the foaming agent described later is improved, the mixing property of the raw material containing isocyanate is improved, and the appearance of the resulting rigid foam is improved and the mechanical properties are improved. effective.
Propylene oxide is preferably used as the alkylene oxide other than ethylene oxide.

When propylene oxide and ethylene oxide are used in combination, the order of ring-opening addition polymerization of alkylene oxide is preferably propylene oxide first and ethylene oxide later.
By ring-opening addition polymerization in this order, most of the hydroxyl groups of the polyol (B) become primary hydroxyl groups, and the reactivity of the polyol (B) increases, so that the reactivity with the polyisocyanate increases. As a result, the appearance of the resulting rigid foam tends to be favorable, which is preferable. Moreover, it is effective in improving the adhesiveness of the rigid foam obtained at the same time.

  The hydroxyl value of the polyol (B) is 200 to 500 mgKOH / g, and preferably 250 to 480 mgKOH / g. When the hydroxyl value of the polyol (B) is 500 mgKOH / g or less, the amount of alkylene oxide-derived oxyalkylene chains present in the polyol (B) increases, the viscosity of the polyol (B) tends to decrease, and the polyol The mixing property is improved, which is preferable. Moreover, the brittleness of the manufactured rigid foam is reduced, and the adhesiveness is likely to be obtained. Moreover, when the hydroxyl value is 200 mgKOH / g or more, it is easy to ensure the mechanical strength of the obtained rigid foam, and the rigid foam is difficult to shrink, which is preferable.

  The polyol (B) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass of the entire polyol. Within this range, the resulting rigid foam has characteristics such as mechanical strength, heat resistance, and flame retardancy, and the occurrence of cracks and lateral flow is suppressed, and the adhesion between the foam layers is improved.

(Polyol (C))
The polyol of the present invention preferably further contains a polyol (C) in addition to the polyol (A) and the polyol (B).
The polyol (C) is a polyol having a hydroxyl number of 2 to 4 and a hydroxyl value of 25 to 200 mgKOH / g, obtained by ring-opening addition polymerization of an alkylene oxide to a polyhydric alcohol.
That is, the polyol (C) is a polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 2 to 4 hydroxyl groups as an initiator.

  Examples of the initiator used for producing the polyol (C) include ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, diglycerin, pentaerythritol, and the like. Also good. Of these, one or more selected from the group consisting of glycerin, trimethylolpropane, 1,2,6-hexanetriol, diglycerin, and pentaerythritol increase the adhesiveness of the rigid foam, particularly the initial adhesiveness. Is preferable.

As the alkylene oxide used for the production of the polyol (C), ethylene oxide, propylene oxide, butylene oxide and the like can be used. In particular, it is preferable to use propylene oxide and ethylene oxide together.
When propylene oxide and ethylene oxide are used in combination, the order of ring-opening addition polymerization of alkylene oxide is preferably propylene oxide first and ethylene oxide later.

The proportion of propylene oxide is preferably 50 to 95% by mass and more preferably 60 to 90% by mass with respect to the total amount of alkylene oxide used in the production of the polyol (C).
If it is the said ratio, a polyol (C) will have an appropriate reaction activity, and the storage stability will also become favorable and is preferable.
The ratio of the primary hydroxyl group of the polyol (C) is preferably 60 to 100%.

The hydroxyl value of the polyol (C) is 25 to 200 mgKOH / g, and preferably 30 to 120 mgKOH / g. If the hydroxyl value of the polyol (C) is 200 mgKOH / g or less, the amount of alkylene oxide-derived oxyalkylene chains present in the polyol (C) increases, the viscosity of the polyol (C) tends to decrease, and the polyol The mixing property is improved, which is preferable. Moreover, the brittleness of the manufactured rigid foam is reduced, and the adhesiveness is likely to be obtained.
When the hydroxyl value of the polyol (C) is 25 mgKOH / g or more, the resulting rigid foam is difficult to shrink, which is preferable. That is, if it is in the said range, while maintaining the mixing property of a raw material favorable, the adhesive strength of a rigid foam, especially the initial adhesive strength can be made high, and it is preferable.

  The polyol (C) is preferably 0 to 20% by mass, more preferably 2 to 15% by mass, based on the entire polyol. Within this range, the resulting rigid foam has characteristics such as mechanical strength, and the peeling between the substrate and the foam layer is suppressed, and even when an HFC compound is used as a foaming agent, the vapor pressure of the raw material system Can be kept low.

(Other polyol (D))
The polyol of the present invention uses polyol (A) and polyol (B), preferably further polyol (C), and further polyol (D) other than polyol (A), (B) or (C). Can be used.
The proportion of the polyol (D) is preferably 25% by mass or less, more preferably 10% by mass or less of the entire polyol.
Examples of the polyol (D) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. Further, a polymer-dispersed polyol in which polymer fine particles are stably dispersed may be used in combination.
The hydroxyl value of the polyol (D) is preferably 300 to 600 mgKOH / g.

[Polyisocyanate]
In the present invention, the polyisocyanate includes aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; a mixture of two or more of the above polyisocyanates; An isocyanate etc. are mentioned.
Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and the like. These polyisocyanates or their prepolymer-modified products, nurate-modified products, urea-modified products, carbodiimide-modified products, and the like. Of these, crude MDI or a modified product thereof is preferred, and a modified product of crude MDI is particularly preferred.

  The viscosity of the polyisocyanate at 25 ° C. is preferably 50 to 150 mPa · s. If it is this viscosity range, shrinkage | contraction will not generate | occur | produce in the rigid foam obtained, and the operativity at the time of spraying construction by a spray method will become favorable, and it is preferable because the external appearance of the obtained rigid foam can be kept favorable.

The amount of polyisocyanate used is represented by 100 times the number of isocyanate groups with respect to the total number of active hydrogens in the polyol and other active hydrogen compounds (hereinafter, the value represented by 100 times is referred to as “isocyanate index”). ~ 300 is preferred.
Here, in the urethane prescription which mainly uses a urethanization catalyst as a catalyst, the usage-amount of a polyisocyanate compound is an isocyanate index | exponent, 50-170 are preferable and 70-150 are more preferable.
Moreover, in the isocyanurate prescription which mainly uses the catalyst which accelerates | stimulates the trimerization reaction of an isocyanate group as a catalyst, the usage-amount of a polyisocyanate compound is an isocyanate index | exponent, 120-300 are preferable and 150-270 are more preferable. In this invention, it is preferable to employ | adopt urethane prescription from viewpoints, such as adhesiveness, and the said isocyanate index has preferable 50-170.

[catalyst]
Examples of the catalyst used in the present invention include organometallic compounds, carboxylic acid metal salts, tertiary amines and quaternary ammonium salts, and two or more of them can be used in combination.
In the present invention, since a highly reactive polyol is used, the reaction can be carried out without using or hardly using a catalyst comprising a metal compound such as lead, tin, or mercury.

  Examples of organic metal compounds other than lead, tin, and mercury-based compounds include bismuth octoate, bismuth neodecanoate, zinc octoate, zinc neodecanoate, zinc naphthenate, nickel octoate, nickel naphthenate, and cobalt naphthenate. Since metal compounds such as lead, tin, and mercury cause toxicity problems and environmental problems, it is preferable that the amount used is small, and it is more preferable not to use them.

Examples of the carboxylic acid metal salt include alkali metal salts and alkaline earth metal salts of carboxylic acids.
Examples of the carboxylic acid include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid, and adipic acid, aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid, and the like.
Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  As the tertiary amine, for example, 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, tri Ethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpho , N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, and other tertiary amines Compounds.

  Examples of the quaternary ammonium salt include tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxy Examples thereof include tetraalkylammonium organic acid salts such as propyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  When spray foaming is employed as a construction method, it is preferable to use a tertiary amine in combination with a metal compound other than lead, tin, and mercury in order to complete the reaction in a short time. In this case, the metal compound other than lead, tin, and mercury is preferably an organometallic compound, particularly preferably bismuth 2-ethylhexylate or potassium 2-ethylhexanoate.

[Foaming agent]
In the present invention, it is preferable to use water and a hydrofluorocarbon as the foaming agent. As for the usage-amount of the water as a foaming agent, 0.5-5 mass parts is preferable with respect to 100 mass parts of polyols. Moreover, 5-60 mass parts is preferable with respect to 100 mass parts of polyols, and, as for the usage-amount of hydrofluorocarbon, 10-45 mass parts is more preferable.

Examples of the hydrofluorocarbon include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3. , 3-pentafluorobutane (HFC-365mfc), 1,1,2,2-tetrafluoroethyl difluoromethyl ether (HFE-236pc), 1,1,2,2-tetrafluoroethyl methyl ether (HFE-254pc) 1,1,1,2,2,3,3-heptafluoropropyl methyl ether (HFE-347mcc) and the like.
Among these, it is preferable to use one or more selected from the group consisting of HFC-134a, HFC-245fa, and HFC-365mfc.

  Use of the hydrofluorocarbon in combination with water is preferable in that it is easy to obtain a lightweight rigid foam, is excellent in dimensional stability and mechanical properties of the obtained rigid foam, and is excellent in thermal insulation properties of the rigid foam.

[Foam stabilizer]
In the present invention, a foam stabilizer is used to form good bubbles. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. Although the usage-amount of a foam stabilizer may be selected suitably, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compounds.

[Other ingredients]
In the present invention, any compounding agent can be used in addition to the above-described polyol, polyisocyanate, catalyst, foaming agent, and foam stabilizer. Compounding agents include fillers such as calcium carbonate and barium sulfate; anti-aging agents such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, anti-fungal agents, foam breakers, dispersants, discoloration prevention Agents and the like.

[Construction method]
The production method of the present invention is suitable for a construction method requiring a quick reaction, particularly a spray method. The spray method is a foaming method in which a polyol system liquid and a polyisocyanate compound are reacted while sprayed on a construction surface.
Since the spray method directly manufactures rigid foam at a construction site, it has advantages such as being able to suppress construction costs and being able to perform construction on uneven construction surfaces without gaps. Therefore, it is often adopted when constructing a hard foam heat insulating material on a wall, ceiling or the like at a construction site. Specific construction examples include heat insulating materials for condominiums, office buildings, prefabricated refrigerated warehouses, and the like. Especially the manufacturing method of the rigid foam of this invention is suitable for construction of the heat insulating material of a freezer warehouse.
Various methods are known as the spray method, and airless spray foaming in which a polyol and a polyisocyanate are mixed with a mixing head and foamed is particularly preferable.

In the case of having a thick foam layer in which the thickness of the rigid foam layer is 100 mm or more, it is particularly important that the adhesiveness is very high and cracks do not occur. A hard foam layer having such a thickness is difficult to manufacture if only one layer is applied, and a multilayer spraying operation is required.
According to the production method of the present invention, it is excellent in initial adhesiveness and heat insulation performance, and is less likely to cause problems such as lateral flow and cracking. It is. For example, a foam layer of about 100 mm can be obtained by applying four layers of foam layers of less than 30 mm. According to the multilayer spraying, particularly high heat insulation can be achieved.

[Rigid foam]
The density of the rigid foam produced by the production method of the present invention is preferably 25 to 40 kg / m ³ . The density can be adjusted by the amount of the foaming agent and can be reduced by using a large amount of foaming agent. However, if a large amount of foaming agent is used, the obtained rigid foam tends to shrink.
The closed cell ratio of the rigid foam produced by the production method of the present invention is preferably 85% or more. A high closed cell ratio means that the ratio of closed cells formed during the foaming of the rigid foam is high, leading to high heat insulation performance. On the other hand, if the closed cell ratio is low, the cell has air permeability and the heat insulation performance is low. The closed cell ratio can be adjusted to some extent by selecting the type and amount of the foam stabilizer.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The raw materials used in the examples and comparative examples are as follows.

(Polyol (A1))
Polyol A11: A polyether polyol having a hydroxyl value of 350 mgKOH / g, obtained by adding ethylene oxide (hereinafter abbreviated as EO) using 1- (2-aminoethyl) piperazine as an initiator.
Polyol A12: a polyether polyol obtained by adding EO using ethylenediamine as an initiator and having a hydroxyl value of 300 mgKOH / g.
Polyol A13: A hydroxyl value obtained by mixing polyether polyol having a hydroxyl value of 760 mgKOH / g obtained by adding EO using ethylenediamine as an initiator and polyol A11 at a mass ratio of 2: 8. 432 mg KOH / g polyether polyol.

(Polyol (A2))
Polyol A21: A polyether polyol having a hydroxyl value of 300 mgKOH / g, obtained by adding propylene oxide (hereinafter abbreviated as PO) using 1- (2-aminoethyl) piperazine as an initiator.
Polyol A22: A polyether polyol having a hydroxyl value of 350 mgKOH / g, obtained by adding PO with monoethanolamine as an initiator.
Polyol A23: A polyether polyol having a hydroxyl value of 760 mgKOH / g, obtained by adding PO with ethylenediamine as an initiator.
Polyol A24: A polyether polyol having a hydroxyl value of 350 mgKOH / g, obtained by adding PO using ethylenediamine as an initiator.
Polyol A25: A polyether polyol having a hydroxyl value of 550 mgKOH / g, obtained by adding PO using ethylenediamine as an initiator.
Polyol A26: A polyether polyol having a hydroxyl value of 500 mgKOH / g, obtained by ring-opening addition polymerization of PO using monoethanolamine as an initiator.

(Polyol (A3))
Polyol A31: A polyether polyol having a hydroxyl value of 350 mgKOH / g obtained by adding PO and EO in this order using 1- (2-aminoethyl) piperazine as an initiator. The ratio of EO to the total amount of added PO and EO is 60% by mass.

(Polyol (B))
Polyol B1: Obtained by ring-opening addition polymerization of PO and EO in this order using a Mannich compound obtained by reacting 1.4 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol. A polyether polyol having a hydroxyl value of 300 mgKOH / g. The ratio of EO to the total amount of added PO and EO is 60% by mass.
Polyol B2: obtained by ring-opening addition polymerization of PO and EO in this order using a Mannich compound obtained by reacting 2.2 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol. A hydroxyl value of 430 mg KOH / g polyether polyol. The ratio of EO to the total amount of added PO and EO is 24% by mass.
Polyol B3: hydroxyl value 470 mgKOH / obtained by ring-opening addition polymerization of PO with a Mannich compound obtained by reacting 2.2 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol g polyether polyol.

(Polyol (C))
Polyol C1: A polyether polyol having a hydroxyl value of 56 mgKOH / g, obtained by adding PO and EO in this order using glycerol as an initiator. The ratio of EO to the total amount of added PO and EO is 13% by mass.

(Polyol (D))
Polyol D1: A polyether polyol having a hydroxyl value of 300 mgKOH / g, obtained by ring-opening addition polymerization of PO using a mixture of sucrose and glycerin as an initiator (mixing ratio is 1.5: 1 by mass).
Polyol D2: A polyether polyol having a hydroxyl value of 280 mgKOH / g, obtained by ring-opening addition polymerization of EO using bisphenol A as an initiator.

(catalyst)
Tertiary amine catalyst: Triethylenediamine dipropylene glycol solution (trade name: TEDA-L33, manufactured by Tosoh Corporation).
Catalyst A: mineral spirit solution of lead 2-ethylhexanoate (trade name: Nikka Octix Lead 20%, manufactured by Nippon Chemical Industry Co., Ltd.)
Catalyst B: potassium 2-ethylhexanoate (trade name: PACCAT 15G, manufactured by Nippon Chemical Industry Co., Ltd.)
Catalyst C: Bismuth 2-ethylhexylate (Brand name: PACCAT 25, manufactured by Nippon Chemical Industry Co., Ltd.)

(Example of rigid polyurethane foam production)
As Production Examples 1 to 23, rigid foams were produced by the following method using the formulations shown in Tables 1 and 2. Production Examples 1 to 13 are Examples, and Examples 14 to 23 are Comparative Examples. In addition, the numerical value shown in Table 1 and Table 2 is a mass part unless there is particular notice.
In addition, the ratio (EO / AO of the entire polyol) of the ethylene oxide in the alkylene oxide to be subjected to ring-opening addition polymerization for the entire polyol described in Tables 1 and 2 was obtained from the ratio of EO and the blending ratio of each polyol used. . Moreover, the hydroxyl value of polyol (A) was calculated | required from the hydroxyl value and compounding ratio of each polyol (A1), polyol (A2), and polyol (A3) used as polyol (A). Moreover, the ratio (EO / AO) of ethylene oxide in the total alkylene oxide added with polyol (A) is the ratio of EO of each polyol (A1), polyol (A2), and polyol (A3) used as polyol (A). And the blending ratio.

  In each of the polyol mixtures obtained by mixing the polyols shown in Table 1 and Table 2 (100 parts by mass in total), the foaming agent and catalyst of Table 1 and Table 2, and a silicone foam stabilizer (trade name: SH- 193, 1.5 parts by mass of Toray Dow Corning Silicone Co., Ltd. and 15 parts by mass of a flame retardant (tris (2-chloropropyl) phosphate) are added and mixed to obtain a polyol composition (polyol system liquid) did.

(Evaluation of reactivity)
30 g of each polyol system liquid prepared according to Table 1 and Table 2, and 33 g of this and polymethylene polyphenyl polyisocyanate (trade name: MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) : 1) is weighed into a cup, and each liquid temperature is adjusted to 15 ° C., then mixed by hand stirring with a stirring blade adjusted to 3000 rpm until just before cream time (the moment when it becomes transparent). A rigid foam was produced.
As an index of reactivity, cream time (hereinafter referred to as “CT”) and rise time (hereinafter referred to as “RT”) were measured as follows. The results are shown in Tables 1 and 2.
・ CT
The time from immediately after the start of stirring and mixing of the polyol system liquid and the polyisocyanate until the mixed liquid became white and foaming started was defined as CT.
・ RT
The time from immediately after the start of stirring and mixing of the polyol system liquid and the polyisocyanate until the apparent foaming was finished was defined as RT.

(Spray construction test)
The prepared polyol system solution and polyisocyanate are foamed and reacted with a gasmer spray foaming machine (FF-1600) at a liquid temperature of 36 ° C. and a room temperature of 10 ° C., which are the foaming conditions in winter, and hard. A polyurethane foam was produced. The discharge ratio between the polyol system liquid and the polyisocyanate was 1/1.

From the spray foaming machine, spraying was performed on a base material made of a flexible plate having a length of 600 mm, a width of 600 mm, and a thickness of 5 mm fixed to an iron plate jig.
After spraying a lower spray layer of 1 mm in thickness, spraying was performed in three layers so that the thickness of one layer was 25 to 30 mm, and the layers were laminated four times in total. After spraying each layer, the time (interval) until the start of spraying the next layer was 30 seconds.

(Core density)
The core density of the obtained rigid foam was measured according to JIS A9526. The results are shown in Tables 1 and 2.

(Adhesive evaluation)
One day after the construction, the obtained rigid polyurethane foam was peeled off from the substrate, and the adhesion state at the interface between the substrate and the rigid foam layer was observed. The adhesiveness was evaluated by visual observation according to the following criteria. The results are shown in Table 1.
The observation surface is the entire surface of the base material after the hard foam is peeled off. Further, the poorly bonded portion refers to a portion where the rigid foam is hardly adhered on the observation surface (a portion where the rigid foam and the base material have been peeled off before peeling).
1: Adherent defective portions are observed on almost the entire observation surface, and there are some practical problems.
2: 5 or more small adhesion failure portions are observed in the observation surface, and there are some practical problems.
3: Although 1 to 4 small adhesion failure portions are observed in the observation surface, there is no practical impact.
4: Degree of adhesion is not recognized in the observation surface, and is practically excellent.

(Evaluation of lateral flow)
The distance (lateral elongation distance, unit: mm) of the obtained rigid foam extending laterally and protruding from the edge of the substrate was measured, and the lateral flow was evaluated according to the following criteria. The results are shown in Table 1.
X: The lateral elongation distance is 10 mm or more, and there is a problem in practical use and cannot be used.
A: The lateral elongation distance is 5 mm or more and less than 10 mm, and there is little influence in practical use.
A: The lateral elongation distance is less than 5 mm, which is practically excellent.

As shown in Table 1, Production Examples 1 to 13, which are Examples, had high reactivity and good evaluation of adhesiveness and lateral flow as in Production Examples 14 and 15 using a catalyst containing lead. .
On the other hand, as shown in Table 2, the production examples 16 to 23 as comparative examples had low reactivity. Moreover, manufacture examples 19-22 were inferior to evaluation of adhesiveness or a lateral flow. Further, Production Examples 16 to 18 and Production Example 23 were not able to be constructed themselves and could not be evaluated for adhesiveness and lateral flow.

Claims (10)

In the method of producing a rigid foam synthetic resin by reacting a polyol and a polyisocyanate in the presence of a foaming agent, a foam stabilizer and a catalyst, the polyol contains the following polyol (A) and polyol (B), A method for producing a rigid foam synthetic resin, wherein the proportion of ethylene oxide in the total alkylene oxide to be subjected to addition polymerization is 30 to 60% by mass.
Polyol (A): Polyether polyol having a hydroxyl value of 100 to 800 mgKOH / g obtained by ring-opening addition polymerization of alkylene oxide to initiator (S1). Initiator (S1) is composed of aliphatic amine and fat A polyether polyol which is at least one selected from the group consisting of cyclic amines, and the proportion of ethylene oxide in the alkylene oxide to be subjected to ring-opening addition polymerization is 25% by mass or more.
Polyol (B): a polyether polyol having a hydroxyl value of 200 to 500 mgKOH / g obtained by ring-opening addition polymerization of alkylene oxide to initiator (S2). Initiator (S2) is phenols or aldehydes. And a polyether polyol which is a Mannich condensation product obtained by reacting alkanolamines.   The rigid foam synthetic resin according to claim 1, wherein the polyol (A) comprises a polyol (A1) having a hydroxyl value of 100 to 700 mgKOH / g obtained by ring-opening addition polymerization of ethylene oxide to the initiator (S1). Manufacturing method.   The rigid according to claim 1 or 2, wherein the polyol (A) comprises a polyol (A2) having a hydroxyl value of 250 to 800 mgKOH / g obtained by ring-opening addition polymerization of propylene oxide to the initiator (S1). A method for producing foamed synthetic resin.   The method for producing a rigid foam synthetic resin according to any one of claims 1 to 3, wherein the initiator (S1) is ethylenediamine and / or piperazine.   The method for producing a rigid foam synthetic resin according to any one of claims 1 to 4, wherein the polyol (B) has a ratio of ethylene oxide in alkylene oxide to be subjected to ring-opening addition polymerization of 20 to 95% by mass.   The method for producing a rigid foam synthetic resin according to any one of claims 1 to 5, wherein the polyol contains 20 to 80% by mass of the polyol (A) and 5 to 40% by mass of the polyol (B).   2. The polyol further comprises a polyol (C) obtained by ring-opening addition polymerization of an alkylene oxide to a polyhydric alcohol and having a hydroxyl number of 2 to 4 and a hydroxyl value of 25 to 200 mgKOH / g. The manufacturing method of the hard foam synthetic resin in any one of -6.   The method for producing a rigid foam synthetic resin according to any one of claims 1 to 7, wherein the catalyst comprises a compound of a metal other than lead, tin, and mercury, and a tertiary amine.   The manufacturing method of the hard foam synthetic resin in any one of Claims 1-8 by a spray method.   The method for producing a rigid foam synthetic resin according to claim 9, wherein the spraying method is a multilayer spraying method.