JP2018070708A - Rigid polyurethane foam, and three-solution-type premix composition and catalyst composition for producing rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rigid polyurethane foam excellent in quality stability having usage of an expensive amine catalyst reduced when a hydrofluoroolefin (HFO) or a hydrochlorofluoroolefin (HCFO) is used as a foaming agent, three-solution-type premix composition and catalyst composition excellent in storage stability to be suitably used for producing the rigid polyurethane foam.SOLUTION: A rigid polyurethane foam is produced by expanding a mixed solution containing a polyisocyanate compound, a polyol compound, a foaming agent, an organometallic catalyst having foaming ability, and an amine catalyst. The foaming agent contains one or more of HFO and HCFO. The organometallic catalyst is a tin (II) compound. The rigid polyurethane foam is produced by using the three-solution-type premix composition and the catalyst composition.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a rigid polyurethane foam provided in a building or structure for the purpose of imparting heat insulation properties, anti-condensation properties, and the like, and a three-component premix composition and a catalyst composition that are suitably used for the production thereof.

Rigid polyurethane foam is prepared by mixing a polyisocyanate compound having two or more isocyanate groups and a polyol compound having two or more hydroxyl groups together with a foaming agent, a catalyst, a foam stabilizer, and the like to perform a foaming reaction and a resinification reaction. By carrying out simultaneously, it can obtain as a uniform resin foam.
In the production of rigid polyurethane foam, from the viewpoint of facilitating the work, a so-called premix in which a foaming agent, a catalyst, a foam stabilizer, a flame retardant, and the like, which are auxiliary agents, are mixed in advance with a polyol is usually used.

  Conventionally, chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) have been used as foaming agents, but they are now replaced with hydrofluorocarbon (HFC) from the viewpoint of environmental problems due to destruction of the ozone layer. . However, HFC is a greenhouse gas, and in recent years, reduction is required from the viewpoint of global warming countermeasures.

For this reason, hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO) having a double bond in the main chain are attracting attention as new blowing agents that can be adapted to the destruction of the ozone layer and the environmental problems of greenhouse gases. ing. However, HCFO sometimes reacts and decomposes with the amine catalyst generally used with HFC over time, and the amine catalyst sometimes deteriorates.
For this reason, there existed a problem that a foaming agent and a catalyst could not be made to coexist in a premix from a viewpoint of the storage stability of a premix.

  For this, amine catalysts having low reactivity with foaming agents such as HFO and HCFO have been proposed. For example, Patent Document 1 discloses a reaction between an amine catalyst and a foaming agent such as HFO or HCFO by using an oxygen-containing amine catalyst having an alkanolamine, etheramine, or morpholine group as an amine catalyst in the premix. It is described that sex is suppressed.

  Patent Document 2 describes that the catalyst is removed from the premix component and added and mixed separately.

Special table 2014-508838 gazette JP 2009-35628 A

  However, the special amine catalyst as described in Patent Document 1 is expensive and requires a large amount of catalyst due to low reactivity, which increases the production cost of rigid polyurethane foam. Had problems.

On the other hand, a catalyst used for producing a rigid polyurethane foam is required to promote both the foaming reaction and the resinification reaction, that is, the foaming ability and the resinification ability.
In the production of rigid polyurethane foam, an organometallic catalyst may be used in addition to the amine catalyst. However, the amine catalyst is usually used as a catalyst having a foaming ability, and the organometallic catalyst has a resinizing ability. It was selected and used from the viewpoint. In addition, some organometallic catalysts can be hydrolyzed by reacting with water during storage and storage of the premix, and the types of organometallic catalysts that can be used in ordinary two-component mixed rigid polyurethane foams have been limited. .

  Moreover, when removing a catalyst from a premix component, it is necessary to handle only a catalyst independently separately from a premix. However, since the amine catalyst used in the production of rigid polyurethane foam is a strongly basic liquid or vapor, there is a risk of irritation when it comes into contact with eyes or skin. From this viewpoint, the amine catalyst is used in field work. Handling alone is not preferable for safety.

  The present invention has been made to solve the above problems, and when HFO, HCFO, or the like is used as a foaming agent, the amount of expensive amine catalyst used can be reduced, and quality stability can be improved. Provided are a rigid polyurethane foam from which an excellent foam can be safely obtained, and a three-component premix composition and a catalyst composition which can be suitably used for the production of the rigid polyurethane foam and have excellent storage stability. It is for the purpose.

  In the rigid polyurethane foam produced by using HFO, HCFO or the like as a foaming agent, the present invention reduces the amount of expensive amine catalyst used by using a specific metal catalyst having foaming ability as a third component. This is based on the finding that a foam having a good foamed state can be stably obtained.

That is, the present invention provides the following [1] to [15].
[1] A rigid polyurethane foam formed by foaming a mixed liquid containing a polyisocyanate compound, a polyol compound, a foaming agent, an organometallic catalyst having foaming ability, and an amine catalyst, wherein the foaming agent comprises hydrofluoroolefin and A rigid polyurethane foam comprising any one or more of hydrochlorofluoroolefins, wherein the organometallic catalyst is a tin (II) compound.
[2] The rigid polyurethane foam according to the above [1], wherein the tin (II) compound is a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II).
[3] The rigid polyurethane foam according to the above [1] or [2], wherein the tin (II) compound is bis (neodecanoic acid) tin.

[4] A premix composition for producing a rigid polyurethane foam, comprising a liquid A containing an isocyanate compound, a liquid B containing a polyol compound, a blowing agent and an amine catalyst, and C containing an organometallic catalyst having foaming ability. A three-component type in which the foaming agent contains at least one of hydrofluoroolefin and hydrochlorofluoroolefin, and the organometallic catalyst is a tin (II) compound. Premix composition.
[5] The three-component premix composition according to the above [4], wherein the tin (II) compound is a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II).
[6] The three-component premix composition according to the above [4] or [5], wherein the tin (II) compound is bis (neodecanoic acid) tin.

[7] The liquid C has a molecular weight of 150 to 8,000, and a polyoxyalkylene compound, an aromatic monocarboxylic acid ester, an aromatic polycarboxylic acid ester, an aliphatic monocarboxylic acid ester, and an aliphatic polycarboxylic acid ester. The three-component premix composition according to any one of [4] to [6] above, which contains, as a diluent, one or more compounds selected from polyvalent carboxylic acid esters.
[8] The three-component premix composition according to the above [7], wherein the diluent is one or more compounds selected from the following (a) to (c).
(A) A polyether compound having a structure in which the hydroxyl group at one or both ends of the polyoxyalkylene diol is replaced with any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group (b) Polyether Triol Compound which is Polyoxyalkylene Glyceryl Ether (c) Hydroxyl moiety of one or more carboxyl groups of aromatic monocarboxylic acid, aromatic polycarboxylic acid, aliphatic monocarboxylic acid, or aliphatic polycarboxylic acid Is an ester compound having a structure in which any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group is substituted [9] The above-mentioned [7], wherein the diluent is polyoxypropylene monobutyl ether ] Or the three-component premix composition according to [8].

[10] A catalyst composition for producing a rigid polyurethane foam, comprising an organometallic catalyst having a foaming ability and a diluent, wherein the organometallic catalyst is a tin (II) compound, and the diluent has a molecular weight of 150. 1 to 8,000 and selected from a polyoxyalkylene compound, an aromatic monocarboxylic acid ester, an aromatic polycarboxylic acid ester, an aliphatic monocarboxylic acid ester, and an aliphatic polycarboxylic acid ester A catalyst composition, which is a compound of more than one species.
[11] The catalyst composition according to [10], which is used together with a blowing agent containing at least one of hydrofluoroolefin and hydrochlorofluoroolefin.
[12] The catalyst composition according to [10] or [11], wherein the tin (II) compound is a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II).
[13] The catalyst composition according to any one of [10] to [12], wherein the tin (II) compound is bis (neodecanoic acid) tin.

[14] The catalyst composition according to any one of [10] to [13], wherein the diluent is one or more compounds selected from the following (a) to (c).
(A) A polyether compound having a structure in which the hydroxyl group at one or both ends of the polyoxyalkylene diol is replaced with any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group (b) Polyether Triol Compound which is Polyoxyalkylene Glyceryl Ether (c) Hydroxyl moiety of one or more carboxyl groups of aromatic monocarboxylic acid, aromatic polycarboxylic acid, aliphatic monocarboxylic acid, or aliphatic polycarboxylic acid Is an ester compound having a structure in which any one group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group is substituted [15] The above [10], wherein the diluent is polyoxypropylene monobutyl ether ] The catalyst composition of any one of [14].

According to the present invention, when HFO or HCFO is used as a foaming agent, the amount of expensive amine catalyst used can be reduced, and a rigid polyurethane foam from which a foam having excellent quality stability can be obtained safely. Can be provided.
Moreover, according to this invention, the three-component premix composition and catalyst composition which can be used suitably for manufacture of the said rigid polyurethane foam and were excellent in storage stability are provided.

It is the schematic diagram which showed an example of the manufacturing process of the rigid polyurethane foam of this invention.

  Hereinafter, the rigid polyurethane foam of the present invention, and the three-component premix composition and catalyst composition for producing the rigid polyurethane foam will be described in detail.

[Rigid polyurethane foam]
The rigid polyurethane foam of the present invention is a rigid polyurethane foam formed by foaming a mixed liquid containing a polyisocyanate compound, a polyol compound, a foaming agent, an organometallic catalyst having foaming ability, and an amine catalyst. The foaming agent contains one or more of HFO and HCFO, and the organometallic catalyst is a tin (II) compound.
The rigid polyurethane foam is formed by foaming with a specific organometallic catalyst having foaming ability as the main catalyst, and the amount of expensive amine catalyst applicable when the foaming agent is HFO or HCFO is reduced. And can be stably obtained as a foam in a good foamed state.

(Polyisocyanate compound)
The polyisocyanate compound is an isocyanate compound having two or more isocyanate groups, and produces a polyurethane resin by a polyaddition reaction with the polyol compound in the B liquid.
The content of the polyisocyanate compound in the mixed solution before foaming is preferably 20 to 70% by mass, more preferably 30 to 65% by mass, and still more preferably 40 from the viewpoint of the production efficiency of the rigid polyurethane foam. -60 mass%.

The polyisocyanate compound may be either an aromatic polyisocyanate or an aliphatic polyisocyanate, and one of these may be used alone, or two or more may be used in combination.
Specific examples of the aromatic polyisocyanate include diphenyl ether-2,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, 4,6- Dimethyl-1,3-phenylene diisocyanate, 2,2′-diphenylmethane diisocyanate (2,2′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 4,4′-diphenylmethane diisocyanate (4 , 4'-MDI), polymethylene polyphenyl polyisocyanate (crude MDI or polymeric MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate, m-xylylene diisocyanate and the like. .
The aliphatic polyisocyanate may be either acyclic or alicyclic polyisocyanate, and specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
Among these, from the viewpoints of reactivity and mechanical strength of the rigid polyurethane foam produced, monomeric MDI such as 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, and crude MDI or polymeric MDI is preferable, and among these, crude MDI or polymeric MDI is preferably used from the viewpoint of cost.

(Polyol compound)
A polyol compound is an alcohol compound having two or more hydroxyl groups, and produces a polyurethane resin by a polyaddition reaction with an isocyanate compound.
Examples of the polyol compound include polyester polyols and polyether polyols, and any one selected from these is preferably used, and one kind may be used alone, or two or more kinds may be used in combination. From the viewpoint of imparting flame retardancy, the polyester polyol is preferably more. The number average molecular weight of the polyether polyol and the polyester polyol is preferably 50 to 5,000, more preferably 100 to 3,000, from the viewpoints of reactivity and mechanical strength of the rigid polyurethane foam to be produced. More preferably, it is 200-1,000.
In consideration of reactivity with the polyisocyanate compound, the polyol compound is preferably added in an amount of 40 to 100 parts by mass, more preferably 45 to 95 parts by mass, further preferably 100 parts by mass of the polyisocyanate compound. Is 50 to 75 parts by mass.

Examples of the polyester polyol include ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5- Polyhydric alcohols such as pentanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A, and adipic acid, malonic acid, succinic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid, phthalic acid, terephthalic acid, orthophthalic acid Acid, isophthalic acid, azelaic acid, trimellitic acid, glutaconic acid, α-hydromuconic acid, β-diethylsuccinic acid, hemimellitic acid, 1,4-cyclohexanedi Examples include those obtained by polycondensation with polyvalent carboxylic acids such as carboxylic acids. Moreover, what transesterified polyalkylene terephthalate, such as a polyethylene terephthalate and a polybutylene terephthalate, by the polyhydric diol etc. are mentioned.
Examples of polyether polyols include those obtained by addition polymerization of alkylene oxides such as propylene oxide and ethylene oxide to polyhydric alcohols such as glycol, glycerin, and sorbitol, aromatic amines, and aliphatic amines.

(Foaming agent)
A foaming agent has the effect | action which vaporizes by the heat_generation | fever at the time of a polyisocyanate compound and a polyol compound reacting and producing | generating a polyurethane resin, and foams a polyurethane resin.
As a foaming agent, HFO or HCFO shall be included. These may be used alone or in combination of two or more. HFO and HCFO are foaming agents that are expected to increase in demand in the future in place of HFC from the viewpoint of environmental problems, and the present invention corresponds to such foaming agents. Specifically, trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), And trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).
The foaming agent is preferably added in an amount of 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the polyisocyanate compound, from the viewpoint of appropriately foaming the polyurethane resin. 25 parts by mass.

In addition, the foaming agent may contain conventionally used HFC and water. When the isocyanate group of the polyisocyanate compound reacts with water to generate an amino group, carbon dioxide is generated, which also induces foaming in the initial stage of the polyurethane resin formation reaction. Is preferably included.
However, since water may hydrolyze the polyester polyol when the polyol compound contains the polyester polyol, the content of water is preferably smaller than that of other foaming agents. It is preferable that it is 0.5-20 mass parts with respect to 100 mass parts of said foaming agents other than water, More preferably, it is 1-18 mass parts, More preferably, it is 5-15 mass parts.

(Organic metal catalyst)
The organometallic catalyst is a main catalyst for obtaining the rigid polyurethane foam of the present invention, and has an action of promoting the foaming reaction of the polyurethane resin. For this reason, an organometallic catalyst having foaming ability is used, and in the present invention, a tin (II) compound is used. Among these, it may be used alone or in combination of two or more.
In the present invention, “having foaming ability” means a mixture of 70 to 75 parts by mass of a polyol compound, 3 to 4 parts by mass of water, and 1 part by mass of an organometallic catalyst, and 100 parts by mass of a polyisocyanate compound. For samples that are stirred and uniformly mixed at 15 ° C., the time from the end of stirring until the creamy mixture begins to expand, that is, the cream time (C.T.) is 60 seconds or less. Shall be said. C. is an index of the foaming ability of the organometallic catalyst. T.A. Specifically, it is measured by an evaluation test method described in Examples described later.

As the tin (II) compound, a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II) is particularly preferable. Examples of the aliphatic carboxylic acid include octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, and linolenic acid. Specifically, bis (2-ethylhexanoic acid) tin (II), bis (neodecanoic acid) tin (II) and the like are preferably used, and bis (neodecanoic acid) tin is particularly preferable from the viewpoint of the stability of the compound. (II) is preferred.
The organometallic catalyst is preferably added in an amount of 0.01 to 5 parts by mass, more preferably 0.05 to 100 parts by mass of the polyisocyanate compound, from the viewpoint of the balance between the speed of the foaming reaction and the resinification reaction. -3 parts by mass, more preferably 0.1-1 part by mass.
Note that the organometallic catalyst is sufficiently effective as a main catalyst for promoting the foaming reaction because it is more excellent in foaming ability even if the amount (mass) used is smaller than that of the amine catalyst.

(Amine catalyst)
In the present invention, the tin (II) compound is a catalyst having a foaming ability and acts as a main catalyst. Further, an amine catalyst is used as a co-catalyst to promote the foaming reaction and the resinification reaction. It is done.
However, as described above, when the foaming agent is HFO or HCFO, it is necessary to use a special expensive amine catalyst having low reactivity with these foaming agents, so the amount used should be as small as possible. Is preferred.
As such an amine catalyst, known ones can be used, and those having excellent storage stability even when coexisting with a foaming agent such as HFO or HCFO are preferred. For example, dimethylethanolamine, triethylenediamine, methyldicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, diethylmethylbenzenediamine, 1,2-dimethylimidazole, 1,4-diazabicyclo [2 2.2] octane and the like. These may be used alone or in combination of two or more.
The amine catalyst is preferably added in an amount of 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and still more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the polyisocyanate compound. is there.

(Other ingredients)
The mixed solution may contain additives such as a solvent, a foam stabilizer, a flame retardant, a surfactant, a colorant, and an antioxidant as necessary.
The solvent is used as necessary from the viewpoint of uniformly mixing each component, and is a hydrophobic organic solvent, even if it is a water-soluble organic solvent, as long as it does not reduce the foaming ability of the organometallic catalyst. It may be a solvent. For example, ethylene glycol, propylene glycol, dipropylene glycol and the like can be mentioned. These may be included in commercially available amine catalyst products. Moreover, as a solvent, the diluent of the organometallic catalyst mentioned later may be contained.
As the foam stabilizer, those known in the production of rigid polyurethane foams can be used. Silicone foam stabilizers are preferably used, and examples thereof include siloxane-polyalkylene oxide copolymers.
As the flame retardant, those known in the production of rigid polyurethane foams can be used, and examples thereof include non-halogen phosphate ester tricresyl phosphate and halogen-containing phosphate ester trischloropropyl phosphate.
Surfactants, colorants and antioxidants are not particularly limited, and known ones can be used in the production of rigid polyurethane foam.
The content of these additives can be appropriately adjusted according to the desired physical properties of the foam obtained within a range that does not affect the foaming reaction and resinification reaction of the polyurethane resin. The total content of the additives is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and further preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polyisocyanate compound. is there.

[Three-component premix composition]
The three-component premix composition of the present invention is a premix composition for producing a rigid polyurethane foam, and can be suitably used for producing the rigid polyurethane foam. The three liquids of the premix composition consist of a liquid A containing an isocyanate compound, a liquid B containing a polyol compound, a foaming agent and an amine catalyst, and a liquid C containing an organometallic catalyst having foaming ability. The agent contains one or more of HFO and HCFO, and the organometallic catalyst is a tin (II) compound.
The A liquid, B liquid, and C liquid of these three-component premix compositions can be easily prepared by mixing a predetermined amount of the compounding components in each liquid. If these premix compositions are used as raw materials for producing rigid polyurethane foam, the handling of raw materials and the adjustment of the blending amount of each raw material component are facilitated even in the on-site foaming.
In addition, the isocyanate compound in the A liquid, the polyol compound in the B liquid, the foaming agent and the amine catalyst, and the organometallic catalyst having the foaming ability in the C liquid are those described in the explanation of the hard polyurethane foam. Therefore, the description in the following description of the three-component premix composition is omitted.

<Liquid A>
A liquid is a liquid which contains a polyisocyanate compound as a main component. In addition to the polyisocyanate compound, the liquid A may contain a solvent and an additive such as a foam stabilizer as necessary.
However, from the viewpoint of production efficiency and the like, the content of the polyisocyanate compound in the liquid A is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 97 to 100% by mass. is there.

<Liquid B>
B liquid is a liquid which has a polyol compound as a main component and further contains a foaming agent and an amine catalyst as a promoter. In addition to the polyol compound, the foaming agent, and the amine catalyst, the liquid B may contain a solvent and additives such as the above-described foam stabilizer, flame retardant, colorant, and antioxidant as necessary. .
However, from the viewpoint of production efficiency and the like, the content of the polyol compound in the liquid B as the main component is preferably 40 to 75% by mass, more preferably 45 to 70% by mass, and still more preferably 50 to 65%. % By mass.
Among the components of the premix composition of the B liquid, in particular, the amine catalyst has many skin irritation or skin corrosive properties, and needs attention in handling alone, but is premixed in the premix. Thus, it is possible to improve safety during field work.

<C liquid>
C liquid is a liquid containing as a main component an organometallic catalyst having a foaming ability as a main catalyst.
Using a catalyst having such foaming ability as a third component separately from the polyisocyanate compound and polyol compound, which are polyurethane resin raw materials, and adjusting the amount of mixture, a foam with a good foamed state can be stabilized. Can be obtained.
The organometallic catalyst is preferably added in an amount of 0.05 to 1 part by mass with respect to 100 parts by mass of the B liquid, more preferably 0.08 to 0.0. 8 parts by mass, more preferably 0.1 to 0.5 parts by mass is added.

The liquid C premix composition includes a diluent (solvent) that enables the organometallic catalyst to be supplied as a solution. In addition, additives such as antioxidants may be included as necessary.
However, from the viewpoint of production efficiency and solubility of the organometallic catalyst, the content of the organometallic catalyst in the liquid C is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, More preferably, it is 5-15 mass%. Further, the content of the additive is set to an amount that does not affect the foaming ability of the organometallic catalyst.

(Diluent)
The diluent of the organometallic catalyst is a polyoxyalkylene compound, an aromatic monocarboxylic acid ester, an aromatic polycarboxylic acid ester, an aliphatic monocarboxylic acid ester, or an aliphatic polycarboxylic acid ester, and has a molecular weight of 150 to 8,000 solvents are preferred. These compounds may be used alone or in combination of two or more.
The molecular weight is more preferably 200 to 7,000, still more preferably 300 to 6,000. In addition, the molecular weight said here refers to a number average molecular weight in a polymer compound.
The compound is suitable because it can dissolve the organometallic catalyst and has low water absorption, so that hydrolysis of the organometallic catalyst is suppressed. Moreover, if it is the molecular weight within the said range, C liquid can be maintained at the viscosity which does not have a trouble in mixing with B liquid.

Of the solvent compounds, polyether compounds having a structure in which the hydroxyl group at one or both ends of the polyoxyalkylene diol is replaced with an alkyloxy group or alkyleneoxy group having 3 or more carbon atoms are preferably used. When the polyether compound has a structure in which the hydroxyl groups at both ends of the polyoxyalkylene diol are replaced, the substituted alkyloxy groups or alkyleneoxy groups may be the same or different.
Specific examples of the polyether compound include polyoxypropylene monobutyl ether, triethylene glycol monobutyl ether, polyoxyethylene polyoxypropylene monobutyl ether, polyoxyalkylene monobutyl ether, and the like. In the case of the compound (II), polyoxypropylene monobutyl ether is more preferable from the viewpoint of suppressing that the tin is oxidized from divalent to more stable tetravalent and the foaming ability is lowered.

As the solvent compound, a polyether triol compound which is polyoxyalkylene glyceryl ether is also preferably used.
Specific examples of the polyether triol compound include polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, and polyoxyethylene polyoxypropylene glyceryl ether.

The solvent compound may be an aromatic monocarboxylic acid, an aromatic polycarboxylic acid, an aliphatic monocarboxylic acid, or a hydroxyl group of one or more carboxyl groups of the aliphatic polycarboxylic acid having 3 carbon atoms. An ester compound having a structure in which the above alkyloxy group or alkyleneoxy group is substituted is also preferably used. When the ester compound is an aromatic polyvalent carboxylic acid or an aliphatic polyvalent carboxylic acid and has a structure in which the hydroxyl groups of two or more carboxyl groups are replaced, the replaced alkyloxy groups or alkyleneoxy groups are the same. It may be different or different.
Specific examples of the ester compound include diisononyl phthalate, dioctyl phthalate, diisodecyl phthalate, dibutyl phthalate, dioctyl adipate, diisononyl adipate, and the like. In particular, the organometallic catalyst is a tin (II) compound. In this case, diisononyl phthalate is more preferable from the viewpoint of suppressing the oxidation of tin from divalent to more stable tetravalent and lowering the foaming ability.

[Catalyst composition]
The catalyst composition of the present invention is a catalyst composition for producing a rigid polyurethane foam, and can be suitably used for producing the rigid polyurethane foam. Moreover, it can use suitably as a premix composition of C liquid among the said 3 liquid type premix compositions. The catalyst composition includes an organometallic catalyst having a foaming ability and a diluent, the organometallic catalyst is a tin (II) compound, the diluent has a molecular weight of 150 to 8,000, and , A polyoxyalkylene compound, an aromatic monocarboxylic acid ester, an aromatic polycarboxylic acid ester, an aliphatic monocarboxylic acid ester, and an aliphatic polycarboxylic acid ester.
The catalyst composition can be easily prepared by mixing a predetermined amount of blending components in the catalyst composition. If this catalyst composition is used as a raw material for producing a rigid polyurethane foam, it is easy to adjust the blending amount of the catalyst composition in accordance with the foamed state of the polyurethane resin even in the on-site foaming. Moreover, it can be stably stored and stored without reducing the foaming ability of the organometallic catalyst.
In addition, about the organometallic catalyst which has a foaming ability, it is the same as that of what was described in description of C liquid of said rigid polyurethane foam and a 3 liquid type premix composition, and about the compound used for a diluent. Since it is the same as that described in the description of the liquid C of the three-component premix composition, description in the catalyst composition is omitted.

[Production method of rigid polyurethane foam]
The rigid polyurethane foam of the present invention can be produced in a factory, but can also be produced easily and efficiently even in in-situ foaming.
“In-situ foaming” as used herein refers to bringing the raw material liquid and on-site foaming machine of rigid polyurethane foam to the site where there is a building or structure where it is necessary to provide rigid polyurethane foam for the purpose of heat insulation, etc. It means a construction method for foam molding of rigid polyurethane foam on the spot. Specific methods include a spray method and an injection method. In the present invention, from the viewpoint of ease of construction and the like, the spray method, that is, on-site blowing foaming is preferable.

In FIG. 1, the outline | summary of an example of the manufacturing process of the rigid polyurethane foam of this invention in an in-situ foaming is shown. The manufacturing process shown in FIG. 1 uses the three-component premix composition of the present invention as a raw material for manufacturing a rigid polyurethane foam.
Liquid A containing an isocyanate compound is in liquid A tank 1, liquid B containing a polyol compound, a blowing agent and an amine catalyst is in liquid B tank 2, and liquid C containing an organometallic catalyst having foaming ability (catalyst composition) ) Are stored in the C liquid tank 3, respectively. The in-situ foaming machine 5 is connected to a line through which the liquid A is supplied from the liquid A tank 1 by the liquid supply pump P1, and separately from this, the liquid B is supplied from the liquid B tank 2 by the liquid supply pump P2. Connected. Then, the C liquid is supplied from the C liquid tank 3 to the B liquid line by the liquid feed pump P3, and the supply amount thereof can be adjusted by the mixing adjustment valve 4.
From the viewpoint of uniformly mixing the organometallic catalyst, the liquid C may be foamed using an inert gas such as nitrogen gas, creamed, and mixed with the liquid B. .
By supplying the A liquid, the B liquid, and the C liquid (catalyst composition) in this manner, immediately after the B liquid and the C liquid are mixed, the mixed liquid and the A liquid are mixed in an in-situ foaming machine. Thus, foaming can be performed. According to such a method, the mixing amount of the liquid C can be appropriately adjusted according to the foaming state according to the site environment, and the safety of the site work is also ensured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.

[Test 1] Foaming ability evaluation test of organometallic catalyst (1)
About the various organometallic catalysts shown in the following Table 1, foaming ability was evaluated using a polyisocyanate test liquid (A liquid sample) and a polyol test liquid (B 'liquid sample). For comparison, the same evaluation was performed for the amine catalyst. The compound used for the catalyst for evaluation and the composition of each test solution are shown below.
<Liquid A sample>
(Polyisocyanate compound)
Polymethylene polyphenyl polyisocyanate (polymeric MDI); “Millionate (registered trademark) MR-200”, manufactured by Tosoh Corporation; 52.0 g
<B 'liquid sample>
(Polyol compound)
Aromatic polyester polyol; “Maximol (registered trademark) RDK-133”, manufactured by Kawasaki Kasei Kogyo Co., Ltd .; 36.5 g
(Foaming agent)
・ Water; 2.0g
(Foam stabilizer)
Siloxane-polyalkylene oxide copolymer; “NIAX ^* (registered trademark) SILICON L-6186NT”, manufactured by Momentive Performance Materials Japan GK; 1.0 g
(Flame retardants)
Trischloropropyl phosphate; “TMCPP”, manufactured by Daihachi Chemical Industry Co., Ltd .; 10.0 g
<Catalyst>
(Organic metal catalyst)
・ Bis (neodecanoic acid) tin (II); “Neostan U-50”, manufactured by Nitto Kasei Co., Ltd. ・ Bis (2-ethylhexanoic acid) tin (II); “Neostan U-28”, manufactured by Nitto Kasei Co., Ltd. Bis (2-ethylhexanoic acid) lead (II); “Nikka Octix lead 17% DINP”, manufactured by Nippon Chemical Industry Co., Ltd., Tris (2-ethylhexanoic acid) bismuth (III); “Pucat 25”, Nippon Chemical Sangyo Co., Ltd., dibutyltin maleate (IV); “T-52NJ”, Katsuta Chemical Industries, Ltd. (amine catalyst)
・ Amine catalyst for HFO blowing agent: acid block amine salt; “Polycat (registered trademark) 201”, manufactured by Air Products Japan Co., Ltd. ・ Amine catalyst for HFC blowing agent: polyethylene polyamine (tertiary amine); “TOYOCAT (registered trademark) ) -TT ", manufactured by Tosoh Corporation

<Evaluation test method>
The evaluation test of foaming ability was performed as follows.
0.5 g of each catalyst shown in Table 1 below (1.0 part by mass with respect to 100 parts by mass of the B ′ sample liquid) was added to 49.5 g of the B ′ liquid sample, and the temperature was kept at 15 ° C. for 5 to 10 minutes. A liquid sample 52.0 g was also kept at 15 ° C. for 5 to 10 minutes. Each of these liquid samples was put into a 500 ml polypropylene cup made of polypropylene and mixed and stirred at 3000 rpm for 10 seconds.
The time (C.T.) from the end of stirring until the creamy mixture started to expand was measured. This C.I. T.A. Was used as an index of the foaming ability of the catalyst.
The evaluation test results are shown in Table 1 below.

From the results shown in Table 1, organometallic catalysts (samples 1 and 2), which are tin (II) compounds, are lead (II) compounds (sample 3), bismuth (III) compounds (sample 4), and tin (IV). More than the compound (sample 5) C.I. T.A. It can be said that the organometallic catalyst is short and has an excellent foaming ability. In addition, compared with the amine catalyst for HFO blowing agent (sample 6), C.I. T.A. Is 1/3 or less, and it can be said that it has excellent foaming ability at the same level as the amine catalyst for HFC blowing agent (sample 7).
The amine catalyst for HFO blowing agent (Sample 6) belongs to Category 1 in the skin corrosivity test based on GHS (Globally Harmonized System of Classification and Labeling of Chemicals) category, and has high skin corrosivity. From the viewpoint of safety during work, it is not preferable to handle it alone.

[Test 2] Evaluation test of dilute solution of organometallic catalyst Bis (neodecanoic acid) tin (II) (sample 1) used in sample 1 of test 1 above is a representative example of an organometallic catalyst, which is used for dilution. The liquid was evaluated. Each diluent used for the diluent is shown below.
<Diluent>
Polyoxypropylene monobutyl ether; “New Pole LB-65”, manufactured by Sanyo Chemical Industries, Ltd .; viscosity 13.8 mPa · s (25 ° C.); number average molecular weight 340 (value determined from hydroxyl value)
Polyoxypropylene glyceryl ether; “Sanix GP-3000”, manufactured by Sanyo Chemical Industries, Ltd .; viscosity 485 mPa · s (25 ° C.); number average molecular weight 3,000 (value determined from hydroxyl value)
Polyoxyethylene polyoxypropylene glyceryl ether; “DKS Propyran 353”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; viscosity 891 mPa · s (25 ° C.); number average molecular weight 5,000 (value determined from hydroxyl value)
Diisononyl phthalate; “DINP” manufactured by Taoka Chemical Industries, Ltd .; viscosity 55.5 mPa · s (25 ° C.); molecular weight 419
Trischloropropyl phosphate; “TMCPP”, manufactured by Daihachi Chemical Industry Co., Ltd .; viscosity 69.0 mPa · s (25 ° C.); molecular weight 328
Dipropylene glycol; “DPG”, manufactured by ADEKA Corporation; viscosity 81.2 mPa · s (25 ° C.); molecular weight 134

<Evaluation test method>
The evaluation test was performed as follows.
An organometallic catalyst (bis (neodecanoic acid) tin (II)) prepared by diluting with each diluent shown in Table 2 below, 40 ml of an organometallic catalyst diluent having a concentration of 10% by mass was placed in a 50 ml glass bottle and sealed. It stored at room temperature (25-27 degreeC), and the time-dependent change of the liquid state in a glass bottle was evaluated by visual observation.
The evaluation test results are shown in Table 2 below.

As shown in Table 2, when trischloropropyl phosphate (sample 12) or dipropylene glycol (sample 13) was used as a diluent, the liquid became cloudy by 1 day and precipitation occurred after 2 days. It was. This precipitate is presumed to be a decomposition product of bis (neodecanoic acid) tin (II) which is an organometallic catalyst.
On the other hand, when polyoxypropylene monobutyl ether (sample 8), polyoxyalkylene glyceryl ether (samples 9 and 10), or diisononyl phthalate (sample 11) is used as a diluent, the liquid state is at least 14 days. The transparent state was maintained. Therefore, it can be said that the diluted solution of these organometallic catalysts can be stored and stored stably for a long period of time. In Table 2, “-” in the column 28 days after polyoxyalkylene glyceryl ether (Samples 9 and 10) means that it has not been evaluated.

[Test 3] Evaluation Test of Organometallic Catalyst Diluent (Catalyst Composition) Using the A liquid sample, the B liquid sample, and each C liquid (catalyst composition) sample shown in Table 3 below, the foamed state was evaluated. . The formulation composition of the B liquid sample and the compound used for the C liquid sample are shown below. The liquid A sample is the same as in Test 1.
<B liquid sample>
(Polyol compound)
Aromatic polyester polyol; “Maximol (registered trademark) RDK-133”, manufactured by Kawasaki Kasei Kogyo Co., Ltd .; 12.00 g
Aliphatic amine-based polyether polyol; “SANNICS NL-300”, manufactured by Sanyo Chemical Industries, Ltd .; 7.00 g
Polyether polyol; “DK polyol 3776”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; 10.95 g
(Foaming agent)
・ Water: 0.85g
HCFO blowing agent: trans-1-chloro-3,3,3-trifluoropropene; “Solstice (registered trademark) LBA” manufactured by Honeywell Japan KK; 8.50 g
(Amine catalyst)
-Methyldicyclohexylamine; "Polycat (registered trademark) 12", manufactured by Air Products Japan Co., Ltd .; 1.00 g
1,2-dimethylimidazole / ethylene glycol; “TOYOCAT (registered trademark) DM70”, manufactured by Tosoh Corporation; 1.00 g
(Flame retardants)
Trischloropropyl phosphate; “TMCPP”, manufactured by Daihachi Chemical Industry Co., Ltd .; 8.00 g
(Foam stabilizer)
Siloxane-polyalkylene oxide copolymer; “NIAX ^* (registered trademark) SILICON L-6100NT”, manufactured by Momentive Performance Materials Japan GK; 0.70 g
<Sample C (catalyst composition)>
(Organic metal catalyst)
• Bis (neodecanoic acid) tin (II); “Neostan U-50”, manufactured by Nitto Kasei Co., Ltd. • Bis (2-ethylhexanoic acid) tin (II); “NIAX ^* (registered trademark) D-19”, Momentive・ Performance Materials Japan GK (diluent)
Polyoxypropylene monobutyl ether; same as Sample 8 in Test 2 • Polyoxypropylene glyceryl ether; Same as Sample 9 in Test 2 • Polyoxyethylene polyoxypropylene glyceryl ether; Same as Sample 10 in Test 2 • Diisononyl phthalate; Same as Sample 11 in Test 2

<Evaluation test method>
The evaluation test of the foaming state was performed as follows.
1.00 g of each C liquid sample shown in the following Table 3 obtained by diluting 0.10 g of an organometallic catalyst with 0.90 g of a diluent was added to 50.00 g of the B liquid sample, and kept at 15 ° C. for 5 to 10 minutes. A liquid sample 52.0 g was also kept at 15 ° C. for 5 to 10 minutes. Each of these liquid samples was put into a polypropylene 500 ml death cup and mixed and stirred at 3000 rpm for 2 seconds.
C. from the end of stirring. T.A. Was measured. Further, the time from the start of expansion to the stop, that is, the rise time (bubble rise time; R. T.) was also measured.
Further, a 50 mm × 50 mm × 50 mm foam sample was taken from the top of the rigid polyurethane foam obtained by foaming, the weight was measured, and the density was calculated.
For comparison, the same evaluation test was also performed when the liquid C (catalyst composition) sample was not mixed.
The evaluation test results are shown in Table 3 below.

  From the results shown in Table 3, by diluting the organometallic catalyst tin (II) compound with a predetermined diluent, C.I. T.A. Within 3 seconds and R.I. T.A. Can be said to be about 12 seconds, and it can be said that a foam having a stable density can be formed without causing dripping or insufficient foaming by in-situ foaming. In addition, it is estimated that the same result is obtained when the HFO foaming agent is used.

[Test 4] On-site foaming test <Example 1>
Using the A liquid sample, the B liquid sample, and the C liquid sample having the same composition as the sample 14 of the test 3 above, spray foaming with an in-situ foaming machine capable of mixing each liquid sample in the manner shown in FIG. The foamed state and the finished state of the foam were evaluated. The spraying conditions and the evaluation method are as follows.

(Blowing condition)
-Foaming machine: "HF-1600 type", manufactured by former Gasmer; main heater 33 ° C, hose 30 ° C
・ Blowing object: Slate board (fiber reinforced cement board); 25 ° C
・ Outside temperature humidity: 25 ℃, 53% RH

(Evaluation method)
C. from start of spraying on slate plate T.A. , And the time required from the start of spraying until the liquid does not stick to the hand that touches the foam surface, that is, the tack-free time (TFT) is measured to evaluate the reactivity. did.
Moreover, the finished state of the formed foam was evaluated by visual observation.

<Comparative Example 1>
In Example 1, the C liquid sample was not mixed, and spraying foaming and evaluation were performed in the same manner as in Example 1 except for that.

<Example 2>
In Example 1, instead of blowing and foaming to the slate plate, injection foaming into a 1000 ml death cup (25 ° C.) made of polypropylene was performed, and C.I. T.A. And R.A. T.A. Was evaluated.

<Comparative example 2>
In Example 2, the C liquid sample was not mixed, and other than that, injection foaming and evaluation were performed in the same manner as in Example 2.

  The evaluation results of the above Examples and Comparative Examples are summarized in Table 4.

As can be seen from the results shown in Table 4, when the liquid C sample was mixed (Examples 1 and 2), C.I. T.A. And R.A. T.A. It was observed that the foaming reaction was accelerated. In addition, spray foaming (Example 1) is more preferable than injection foaming (Example 2). T.A. The reason for this is that the heat conductivity of the slate plate to be sprayed is high, and the heat of the sprayed mixed liquid is taken away.
Further, in the case of spray foaming, when the liquid C sample was mixed (Example 1), there was no liquid dripping and the foam surface was smooth. F. T.A. Became shorter. On the other hand, when the liquid C sample was not mixed (Comparative Example 1), dripping occurred, the irregularities were conspicuous on the foam surface, and the smoothness was poor.

1 A liquid tank 2 B liquid tank 3 C liquid tank 4 Mixing adjustment valve 5 On-site foaming machine P1, P2, P3 pump

Claims (15)

A rigid polyurethane foam formed by foaming a mixed liquid containing a polyisocyanate compound, a polyol compound, a foaming agent, an organometallic catalyst having foaming ability, and an amine catalyst,
The foaming agent contains any one or more of hydrofluoroolefin and hydrochlorofluoroolefin,
A rigid polyurethane foam, wherein the organometallic catalyst is a tin (II) compound.   The rigid polyurethane foam according to claim 1, wherein the tin (II) compound is a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II).   The rigid polyurethane foam according to claim 1 or 2, wherein the tin (II) compound is bis (neodecanoic acid) tin. A premix composition for producing rigid polyurethane foam,
It consists of three liquids, liquid A containing an isocyanate compound, liquid B containing a polyol compound, a blowing agent and an amine catalyst, and liquid C containing an organometallic catalyst having foaming ability,
The foaming agent contains any one or more of hydrofluoroolefin and hydrochlorofluoroolefin,
A three-component premix composition, wherein the organometallic catalyst is a tin (II) compound.   The three-component premix composition according to claim 4, wherein the tin (II) compound is a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II).   The three-component premix composition according to claim 4 or 5, wherein the tin (II) compound is bis (neodecanoic acid) tin.   The liquid C has a molecular weight of 150 to 8,000, and a polyoxyalkylene compound, an aromatic monocarboxylic acid ester, an aromatic polycarboxylic acid ester, an aliphatic monocarboxylic acid ester, and an aliphatic polycarboxylic acid The three-component premix composition according to any one of claims 4 to 6, comprising at least one compound selected from esters as a diluent. The three-component premix composition according to claim 7, wherein the diluent is one or more compounds selected from the following (a) to (c).
(A) A polyether compound having a structure in which the hydroxyl group at one or both ends of the polyoxyalkylene diol is replaced with any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group (b) Polyether Triol Compound which is Polyoxyalkylene Glyceryl Ether (c) Hydroxyl moiety of one or more carboxyl groups of aromatic monocarboxylic acid, aromatic polycarboxylic acid, aliphatic monocarboxylic acid, or aliphatic polycarboxylic acid An ester compound having a structure in which is replaced with any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group   The three-component premix composition according to claim 7 or 8, wherein the diluent is polyoxypropylene monobutyl ether. A catalyst composition for producing rigid polyurethane foam, comprising:
An organometallic catalyst having a foaming ability and a diluent,
The organometallic catalyst is a tin (II) compound;
The diluent has a molecular weight of 150 to 8,000, and a polyoxyalkylene compound, an aromatic monocarboxylic acid ester, an aromatic polycarboxylic acid ester, an aliphatic monocarboxylic acid ester, and an aliphatic polycarboxylic acid A catalyst composition, which is one or more compounds selected from esters.   The catalyst composition according to claim 10, wherein the catalyst composition is used together with a blowing agent containing at least one of hydrofluoroolefin and hydrochlorofluoroolefin.   The catalyst composition according to claim 10 or 11, wherein the tin (II) compound is a dicarboxylic acid salt of an aliphatic carboxylic acid having 6 to 20 carbon atoms and tin (II).   The catalyst composition according to any one of claims 10 to 12, wherein the tin (II) compound is bis (neodecanoic acid) tin. The catalyst composition according to any one of claims 10 to 13, wherein the diluent is one or more compounds selected from the following (a) to (c).
(A) A polyether compound having a structure in which the hydroxyl group at one or both ends of the polyoxyalkylene diol is replaced with any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group (b) Polyether Triol Compound which is Polyoxyalkylene Glyceryl Ether (c) Hydroxyl moiety of one or more carboxyl groups of aromatic monocarboxylic acid, aromatic polycarboxylic acid, aliphatic monocarboxylic acid, or aliphatic polycarboxylic acid An ester compound having a structure in which is replaced with any group selected from an alkyloxy group having 3 or more carbon atoms and an alkyleneoxy group   The catalyst composition according to any one of claims 10 to 14, wherein the diluent is polyoxypropylene monobutyl ether.