JP2011026391A - Method for manufacturing spray type hard polyurethane foam - Google Patents

Abstract

（式中、Ｒ_１〜Ｒ_４は、各々独立して、水素原子又はメチル基を表す。ｎは１以上の整数である。）
で示されるアミン化合物からなる群より選ばれる１種又は２種以上のアミン化合物と二酸化炭素との塩からなる発泡性添加剤を用い、かつ触媒として、第３級アミン類、第４級アンモニウム塩類、及びカルボン酸金属塩類（ただし、鉛、錫、水銀の塩を除く。）からなる群より選ばれる１種又は２種以上の触媒を用いる。
【選択図】 なしPROBLEM TO BE SOLVED: To produce a spray-type rigid polyurethane foam capable of suppressing an increase in the amount of an amine catalyst without using a heavy metal catalyst containing highly toxic lead, tin, etc., and achieving improvement of initial foamability and improvement of workability. Provide a method.
In a method for producing a spray-type rigid urethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst, a foaming agent, and, if necessary, an auxiliary agent, Formula (1)
[Chemical 1]

(In the formula, R _{1 to} R ₄ each independently represents a hydrogen atom or a methyl group. N is an integer of 1 or more.)
Tertiary amines and quaternary ammonium salts using as a catalyst a foaming additive comprising a salt of carbon dioxide and one or more amine compounds selected from the group consisting of amine compounds And one or more catalysts selected from the group consisting of carboxylic acid metal salts (excluding salts of lead, tin, and mercury).
[Selection figure] None

Description

  The present invention relates to a method for producing a spray-type rigid urethane foam, and more particularly to a method for producing a rigid polyurethane foam in which initial foamability is improved without using heavy metal catalysts such as lead compounds and tin compounds.

  Polyurethane foams are widely used in furniture, automobile parts, electric refrigerators, building materials and the like because they are excellent in cushioning properties, impact absorption performance, heat insulation properties, and self-adhesion properties.

  In the production of rigid polyurethane foam used as a heat insulating material, conventionally, an organic flon compound has been used as a foaming agent in order to maintain heat insulating performance. However, in recent years, there has been a movement to prohibit their use from the viewpoint of protecting the global environment.

  Specifically, chlorofluorocarbons (CFC) and hydrochlorofluorocarbons (HCFC) with a high global warming potential are not used as blowing agents, and hydrofluorocarbons (HCFC) and hydrofluorocarbons with a low global warming potential ( HFC), hydrocarbons (HC), and a method for producing a rigid polyurethane foam that uses carbon dioxide generated by the reaction of isocyanate and water as a foaming agent has been employed (for example, see Patent Document 1).

  However, the global warming problem has been greatly screamed, and rigid polyurethane foams that use only carbon dioxide, which has a lower global warming coefficient, as the blowing agent without using any organic compounds such as hydrofluorocarbons or hydrocarbons as blowing agents. The demand for manufacturing methods has expanded.

  As a method for producing a rigid polyurethane foam using only carbon dioxide as a foaming agent, for example, it is common to use only water as a foaming agent and utilize carbon dioxide generated by the reaction between water and a polyisocyanate compound. Yes (see, for example, Patent Document 2).

  However, when only water is used as a foaming agent, there is a problem that poor adhesion between the foam and the face material is likely to occur due to an increase in urea bonds due to the reaction between water and isocyanate, and the foam is densified. The problem is pointed out.

  Further, a method of using carbon dioxide in a subcritical fluid, supercritical fluid, or liquid state as a foaming agent (that is, adding liquefied carbon dioxide directly into the formulation) has been proposed (see, for example, Patent Document 3). ).

  Although the method described in Patent Document 3 is suitable for spray-type molding, it has been pointed out that there are poor adhesion in a low temperature atmosphere and problems on the apparatus for using liquid carbon dioxide.

  Furthermore, a method of using an adduct of a primary or secondary amine compound and carbon dioxide as a foaming agent has been proposed (see, for example, Patent Document 4).

  Moreover, although it is not the manufacturing method of the rigid polyurethane foam which uses only a carbon dioxide as a foaming agent, the method of using the salt of a carbon dioxide and amines as a catalyst is known (for example, refer patent document 5).

  However, since the reaction product of carbon dioxide and amines disclosed in Patent Document 4 and Patent Document 5 has a low effect as a foaming agent, the foam has a high density, or the initial foamability in molding by a spray method. However, there is a problem that moldability is deteriorated.

  On the other hand, in spray-type rigid polyurethane foam, polyol and polyisocyanate are reacted in the presence of a catalyst, a foaming agent, and an auxiliary agent such as a foam stabilizer and a flame retardant as necessary, and foam-molded. It is necessary to make the foaming reactivity faster than the problem. That is, in the spray-type hard polyurethane formulation, the reactivity of the foam premix and the polyisocyanate mixed and stirred is sprayed onto the face material and foamed instantaneously so that the foam rapidly gels and hardens. Generally, the initial foaming property (so-called cream time) in the spray formulation is 3 seconds or less, and the gelation time is about 10 seconds.

  Conventionally, in order to enhance the reactivity, heavy metal catalysts such as lead 2-ethylhexanoate and dibutyltin dilaurate (hereinafter sometimes abbreviated as DBTDL) have been used together with amine-based catalysts. However, lead and tin compounds are concerned about the effects on the human body and environment due to their toxicity, and there is a movement to limit their use. If the amount of amine-based catalyst is increased without maintaining the use of heavy metal catalysts such as lead 2-ethylhexanoate and DBTDL, the amount of amine-based catalyst volatilizes and disperses during spraying. It causes deterioration of construction environment such as irritation and odor.

  Reactive amine catalyst with active hydrogen group in the molecule as a method to suppress such eye rainbow phenomenon by amine catalyst (a phenomenon in which amine catalyst in the foam volatilizes and adheres to the human eye to reduce visibility) A method of using is proposed (for example, see Patent Document 6). Moreover, the method of using a bismuth compound as an alternative of a lead compound is proposed (for example, refer patent document 7).

  However, reactive amine catalysts and bismuth compounds have problems such as poor moldability because initial foamability is not sufficient.

  Various studies have been made to solve these problems, but no sufficient solution has yet been found.

JP 2003-89714 A JP 2006-307192 A JP 2002-47325 A JP 2001-52495 A JP 2000-239339 A JP 2009-40961 A JP 2005-307145 A

  The present invention has been made in view of the above background art, and its purpose is to suppress an increase in the amount of amine catalyst without using a heavy metal catalyst containing highly toxic lead, tin, etc. An object of the present invention is to provide a method for producing a spray-type rigid polyurethane foam capable of achieving improvement and improvement in workability.

  As a result of intensive studies to solve these problems, the present inventors use a specific amine compound, a foaming additive that is a salt of carbon dioxide, and a specific catalyst for the production of a spray-type rigid polyurethane foam. As a result, it was found that these problems can be solved, and the present invention has been completed.

  That is, this invention is a manufacturing method of a spray-type rigid polyurethane foam as shown below.

  [1] In a method for producing a spray-type rigid urethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst, a foaming agent, and, if necessary, an auxiliary agent, (1)

（式中、Ｒ_１〜Ｒ_４は、各々独立して、水素原子又はメチル基を表す。ｎは１以上の整数である。）
で示されるアミン化合物からなる群より選ばれる１種又は２種以上のアミン化合物と二酸化炭素との塩からなる発泡性添加剤を用い、かつ触媒として、第３級アミン類、第４級アンモニウム塩類、及びカルボン酸金属塩類（ただし、鉛、錫、水銀の塩を除く。）からなる群より選ばれる１種又は２種以上の触媒を用いることを特徴とするスプレー式硬質ポリウレタンフォームの製造法。

(In the formula, R _{1 to} R ₄ each independently represents a hydrogen atom or a methyl group. N is an integer of 1 or more.)
Tertiary amines and quaternary ammonium salts using as a catalyst a foaming additive comprising a salt of carbon dioxide and one or more amine compounds selected from the group consisting of amine compounds And one or more catalysts selected from the group consisting of carboxylic acid metal salts (excluding salts of lead, tin, and mercury), and a method for producing a spray-type rigid polyurethane foam.

  [2] The method for producing a spray-type rigid polyurethane foam according to the above [1], wherein the amine compound represented by the general formula (1) has a molecular weight of 104 or more.

  [3] Tertiary amines are N, N-dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N′-trimethyl. -N'-hydroxyethylbisaminoethyl ether, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N'-methylpiperazine, N, N-dimethylamino The method for producing a spray-type rigid polyurethane foam according to the above [1] or [2], which is selected from the group consisting of hexanol and 5-dimethylamino-3-methyl-1-pentanol.

  [4] The quaternary ammonium salt is selected from the group consisting of tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, and tetramethylammonium 2-ethylhexanoate. The method for producing a spray-type rigid polyurethane foam as described in any one of [1] to [3] above.

  [5] Any one of the above [1] to [4], wherein the carboxylic acid metal salt is selected from the group consisting of a bismuth salt of a carboxylic acid, a zinc salt of a carboxylic acid, and an alkali metal salt of a carboxylic acid. A method for producing a spray-type rigid polyurethane foam as described in 1.

  [6] Production of spray-type rigid polyurethane foam according to any one of [1] to [5], wherein only the foamable additive and water described in [1] are used as the foaming agent. Law.

  According to the method for producing a spray-type rigid polyurethane foam of the present invention, the foaming start time can be shortened without using lead compounds and tin compounds as catalysts and without increasing the amount of amine catalyst used. Further, the foaming additive used in the production method of the present invention has low odor and low volatility.

  As described above, the production method of the present invention is extremely useful industrially because it can produce a spray-type rigid polyurethane foam having a fast foaming start time without polluting the environment.

  Hereinafter, the present invention will be described in detail.

  The method for producing a spray-type rigid polyurethane foam of the present invention comprises reacting a polyol and a polyisocyanate in the presence of a catalyst, a foaming agent, and, if necessary, an auxiliary such as a foam stabilizer, a flame retardant, etc. In the method for producing a foam, a part or all of the foaming agent comprises a salt of carbon dioxide with one or more amine compounds selected from the group consisting of amine compounds represented by the general formula (1). A foaming additive is used.

  In the said manufacturing method, you may dissolve the salt of the 1 type, or 2 or more types of amine compound chosen from the group which consists of an amine compound shown by the said General formula (1), and a carbon dioxide in a solvent. The salt of an amine compound and carbon dioxide exists as an amine carbonate in the solvent.

  As the amine compound represented by the general formula (1), an amine compound selected from the group consisting of polyoxypropylenediamine having a molecular weight of 104 or more and polyoxyethylenediamine is preferably used. The molecular weight is more preferably in the range of 150 to 500. Moreover, in the said General formula (1), n is a number of the range of 1-35 normally, and the number of the range of 1-9 is still more preferable. If the molecular weight is too small, the carbon dioxide gas generation rate is low, and if the molecular weight is too large, the amount of carbon dioxide added is undesirably small.

  The amine compound of the general formula (1) and the salt of carbon dioxide have a feature that the generation rate of carbon dioxide gas due to thermal decomposition is high.

  The amine compound represented by the general formula (1) can be produced by a conventionally known method. For example, it can be produced by reacting a corresponding molecular weight polypropylene glycol or polyethylene glycol with ammonia at high temperature and pressure.

As the amine compound represented by the general formula (1), specifically, commercially available polyoxypropylene diamines, JEFFAMINE D-230 [in the general formula (1), R ₁ and R _{3 each} represent a methyl group. R ₂ and R ₄ represent a hydrogen atom, n is ˜3.7, and the molecular weight is about 230. CAS No. 9046-10-0] or JEFFAMINE D-400 [In the above general formula (1), R ₁ and R ₃ represent a methyl group, R ₂ and R ₄ represent a hydrogen atom, and n is ˜7.1. Yes, the molecular weight is about 430. CAS No. 9046-10-0] (manufactured by Huntsman). Specific examples of polyoxyethylenediamine include an aminated product of polyethylene glycol (for example, tetraethylene glycol).

  A salt of one or more amine compounds selected from the group consisting of the amine compound represented by the general formula (1) and carbon dioxide (hereinafter sometimes referred to as “amine carbonate”) is, for example, If the amine compound and the solvent are mixed at room temperature and carbon dioxide gas is blown into the mixed solution, the reaction occurs while generating heat, so that the production can be facilitated. The liquid temperature during the reaction is preferably adjusted so as not to exceed 50 ° C., and preferably 40 ° C. or lower. The amount of carbon dioxide added is usually in the range of 0.01 to 0.5 times moles per mole of amino group of the amine compound, but carbon dioxide gas is supplied until carbon dioxide is completely added to the amino group. It is desirable.

  In this case, the solvent is not particularly limited, but water and an organic solvent are preferable, and water and an organic solvent may be used in combination. As the organic solvent, for example, glycols such as ethylene glycol, diethylene glycol, dipropylene glycol, and butanediol, and polyols for urethane production described later are preferable. Of these, water or a mixture of water and glycols is more preferable. Although the usage-amount of a solvent is not specifically limited, It is the range of 0.2-4 times mole normally with respect to 1 mol of amine compounds (namely, amine carbonate to produce | generate). If the amount of the solvent is too small, the solution may become highly viscous.

  In the method for producing a spray-type rigid polyurethane foam of the present invention, the amount of the foaming additive used is usually 0.1 to 20 parts by weight as an amine carbonate when the polyol used is 100 parts by weight. Although it is a range, Preferably it is the range of 0.5-10 weight part.

  As the polyol used in the production method of the present invention, a conventionally known compound can be used, and is not particularly limited. For example, the polyol has two or more reactive hydroxyl groups and has a hydroxyl value of 50 to 1000 mgKOH / g. Polyether polyols, polyester polyols, polymer polyols, phenol polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols.

  Here, as polyether polyol, the compound etc. which added the alkylene oxide to the active hydrogen compound are mentioned, for example. Examples of the active hydrogen compound include polyhydric alcohols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, l, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, glycerin. , Trimethylol bropan, pentaerythritol, methyl glucoside, sorbitol, sucrose, etc., polyphenols (eg, pyrogallol, hydroquinone, etc.), bisphenols (eg, bisphenol A, bisphenol S, bisphenol F, phenol and formaldehyde Low condensate, etc.), aliphatic amines (eg, propylene diamine, hexamethylene diamine, ethylene diamine, diethylene triamine, triethylene tetramine, Tamethylenehexamine, ethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, etc.), aromatic amines (eg aniline, phenylenediamine, xylylenediamine, methylenedianiline, diphenyletherdiamine etc.), alicyclic amines (eg , Isophoronediamine, cyclohexylenediamine, etc.), heteroalicyclic amines (aminoethylpiperazine, etc.), Mannich polyols (for example, compounds obtained by Mannich reaction of polyhydric phenols, aliphatic amines, and formaldehyde) Is mentioned. These polyols can be used alone or in combination of two or more.

  Examples of the alkylene oxide added to the active hydrogen compound include ethylene oxide, propylene oxide, butylene oxide, and combinations of two or more of these. Among these, preferred are ethylene oxide, propylene oxide and combinations thereof.

  The polyester polyol is obtained, for example, by reacting the above-mentioned polyhydric alcohol with a polybasic acid (for example, phthalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid, trimellitic acid, etc.). And a polylactone polyol obtained by ring-opening polymerization of a lactone such as condensed polyester polyol and ε-caprolactone.

  Examples of the polymer polyol include a polymer polyol obtained by reacting the above-described polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. It is done.

  Among these polyols, aliphatic amine-based and aromatic amine-based polyether polyols, Mannich polyols, and phthalic acid-based polyester polyols can be suitably used in the production method of the present invention. The phthalic acid-based polyester polyol is produced by a conventionally known method using phthalic acid such as orthophthalic acid, isophthalic acid, and phthalic anhydride and one or more compounds having two or more hydroxyl groups. And phthalic acid recovered polyester polyols obtained by decomposing phthalic acid polyester molded articles such as polyethylene terephthalate.

  As the polyisocyanate used in the production method of the present invention, conventionally known compounds can be used and are not particularly limited. For example, aromatic polyisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4, Aliphatic polyisocyanates such as 4-dicyclohexylmethane diisocyanate, aromatic polyisocyanates such as xylylene diisocyanate and tetramethylxylylene diisocyanate and modified products thereof (for example, carbodiimide modification, allophanate modification, urea modification, burette modification, isocyanate) Nurate modification, oxazolidone modification, etc.), isocyanate group-terminated prepolymers, and the like.

  Here, examples of the aromatic polyisocyanate include 2,4- or 2,6-toluene diisocyanate (TDI), crude TDI, diphenylmethane 2,4′- or 4,4′-diisocyanate (MDI), and polymethylene polyisocyanate. Phenyl isocyanate (crude MDI) etc. are mentioned.

  In the method for producing a spray-type rigid polyurethane foam of the present invention, these polyisocyanates can be used alone or in combination as appropriate. Among these polyisocyanates, 4,4'-diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI) and modified products thereof are preferred for the production method of spray type rigid polyurethane foam.

  The amount of these polyisocyanates used is INDEX (= [isocyanate group] / [isocyanate group) with an active hydrogen compound (polyol, water, etc.) capable of reacting with the polyisocyanate in consideration of foam strength, completion of the isocyanurate reaction, and the like. Active hydrogen group capable of reaction] (molar ratio) × 100), and a range of 80 to 400 is preferable (hereinafter, this INDEX may be referred to as “isocyanate Index”).

  Examples of the catalyst used in the production method of the present invention include conventionally known tertiary amines, quaternary ammonium salts, and carboxylic acid metal salts containing no lead, tin, or mercury atoms.

  Tertiary amines include, for example, triethylenediamine, dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ ′, N ″ ′-hexamethyltriethylenetetramine, bis (dimethylaminoethyl) ether, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S— Triazine, N-dimethylaminoethyl-N′-methylpiperazine, N, N, N ′, N′-tetramethylhexamethylenediamine, 1,2-dimethylimidazole, N, N-dimethylaminopropylamine, bis (dimethylamino Amine compounds such as propyl) amine, N, N-dimethylaminoethanol, N, N, N′-to Methylaminoethylethanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N- (3-dimethylaminopropyl) -N, N— Examples include alkanolamines such as diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N, N-dimethylaminohexanol, and 5-dimethylamino-3-methyl-1-pentanol. Among these, N, N-dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine having a hydroxyl group reactive with isocyanate or a primary or secondary amino group in the molecule, 2- (2 -Dimethylaminoethoxy) ethanol, N, N, N'-trimethyl-N'- Droxyethylbisaminoethyl ether, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N, N-dimethylaminohexanol, 5 -Dimethylamino-3-methyl-1-pentanol, N, N-dimethylaminopropylamine, and bis (dimethylaminopropyl) amine have less odor and irritation to the spray foam, and also have good initial foamability. More preferred.

  Examples of the quaternary ammonium salts include tetraalkylammonium organic acid salts and hydroxyalkyl quaternary ammonium organic acid salts. Tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate Tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate and the like. Of these, tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, and tetramethylammonium 2-ethylhexanoate are preferred because of their high isocyanurate activity.

  The carboxylic acid metal salt is not particularly limited as long as it is a metal salt other than lead, tin, and mercury, but bismuth salt of carboxylic acid, zinc salt of carboxylic acid, and alkali metal salt of carboxylic acid are preferable. Among these, bismuth octoate, bismuth neodecanoate, zinc octoate, zinc neodecanoate, zinc naphthenate, potassium acetate, and potassium 2-ethylhexanoate are more preferable because of their high activity. Furthermore, potassium acetate and potassium 2-ethylhexanoate are particularly preferable because of high isocyanurate activity.

  The amount of these catalysts used is not particularly limited, but is generally in the range of 0.1 to 10 parts by weight for tertiary amines and 0 for quaternary ammonium salts with respect to 100 parts by weight of polyol. The range of 0.1 to 5 parts by weight, and the range of 0.1 to 5 parts by weight for carboxylic acid metal salts is preferably used.

  As the foaming agent, for example, conventionally known organic compounds and water can be used in addition to the above-described foaming additive, and these may be used in combination. Examples of the organic compounds include fluorine compounds, which are hydrofluorocarbons (HFC), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3. , 3-pentafluorobutane (HFC-365mfc) is preferred. From the viewpoint of global warming, water is the most preferred blowing agent. The amount of water used is not particularly limited because it is appropriately changed depending on the desired density and the amount of amine carbonate used. For example, 1 part by weight of water with respect to 100 parts by weight of polyol. It is preferable to use the above. More preferably, it is 3 parts by weight or more of water with respect to 100 parts by weight of polyol.

  In the manufacturing method of this invention, auxiliary agents other than the above, such as a foam stabilizer and a flame retardant, can be used as needed.

  What is necessary is just to use what is generally used in this field | area as a foam stabilizer, Although it does not specifically limit, For example, nonionic, such as an organopolysiloxane-polyoxyalkylene copolymer and a silicone-glycol copolymer System surfactants, or a mixture thereof. The amount used is not particularly limited, but is usually in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of polyol.

  What is necessary is just to use what is generally used in this field as a flame retardant, For example, phosphate esters, such as tricresyl phosphate, tris chloroethyl phosphate, tris chloropropyl phosphate, etc. Examples include halogen-containing phosphates, halogen-containing organic compounds such as dibromopropanol, dibromoneopentyl glycol, and tetrabromobisphenol A, and inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. Of these, halogen-containing phosphates are preferred, and trischloropropyl phosphate is particularly preferred because of its good stability and high flame retardancy.

  The amount of these flame retardants used varies depending on the required flame retardancy and is not particularly limited. However, in consideration of the balance between flame retardancy and foam strength, 5 to 500 parts by weight with respect to 100 parts by weight of polyol. A range of parts by weight is preferred. When the amount of the flame retardant is large, the flame retardancy is improved, but when it is added excessively, the foam strength may be lowered.

  Further, if necessary, a thickener, a crosslinking agent or a chain extender, a colorant, an anti-aging agent, and other known additives can be further used.

  In the production method of the present invention, for example, the above-mentioned foaming additive, catalyst, foaming agent and the like are mixed in a polyol to obtain a premix liquid, and two liquids of the premix liquid and the polyisocyanate liquid are used with a spray machine. By mixing and spraying, a foamed rigid polyurethane foam can be produced.

The rigid polyurethane foam obtained by the production method of the present invention has a density of usually 10 to 500 kg / m ³ , preferably 20 to 100 kg / m ³ , and a thermal conductivity of usually 40 mW / m · K. The foam physical properties are as follows and the 10% compressive strength is usually about 3.0 kg / cm ² (when the foam density is around 50 kg / m ³ ). The rigid polyurethane foam obtained by the manufacturing method of the spray type rigid polyurethane foam of this invention is used suitably as a heat insulating material, for example.

  Hereinafter, although demonstrated based on an Example and a comparative example, this invention is limited to only these Examples and is not interpreted. In addition, (%) in a table | surface represents% of weight basis unless there is a notice.

Preparation Examples 1 to 3
<Production of salt of amine compound and carbon dioxide (amine carbonate)>
As shown in Table 1, a 500 ml three-necked flask equipped with a stirrer was charged with 235 g of an amine compound in Preparation Example 1 and 175 g of an amine compound in Preparation Examples 2 and 3 and an appropriate amount of pure water or a solvent. Carbon gas was bubbled into the liquid for 3 hours to produce an aqueous solution of the amine carbonate (C-1 to C-2) of the present invention and the amine carbonate (C-3) of the comparative example. Heat generation due to the reaction between the amine compound and carbon dioxide was completed in 1 hour. 200 g of the resulting amine carbonate aqueous solution was sampled and used for the following analysis and evaluation as a foaming agent for urethane.

  The component concentration [composition (% by weight)] in the amine carbonate aqueous solution is also shown in Table 1.

  In addition, the amine carbonate (C-1) of the present invention used in Example 10 is obtained by repeating the preparation of Preparation Example 1 three times to obtain a required amount of 1100 g.

ここで、二酸化炭素の成分濃度は、各アミン炭酸塩水溶液をナトリウムメトキシド溶液（０．１Ｎメタノール溶液）にて滴定分析して求めた。また、アミン化合物と水及び溶剤の濃度は、仕込み量から計算して求めた。

Here, the component concentration of carbon dioxide was determined by titrating analysis of each amine carbonate aqueous solution with a sodium methoxide solution (0.1N methanol solution). Moreover, the density | concentration of an amine compound, water, and a solvent calculated | required from the preparation amount.

Example 1 to Example 9, Comparative Example 1 to Comparative Example 9.
<Manufacture of rigid polyurethane foam>
Polyol A, polyol B, foam stabilizer, flame retardant, catalyst A to catalyst H, water, and amine carbonate aqueous solution were mixed at the quantitative ratio shown in Table 2 to prepare a premix solution. 65 g of this premix solution was placed in a 300 ml polyethylene cup and the temperature was adjusted to 5 ° C. To this 300 ml polyethylene cup, the amount of polyisocyanate shown in Table 2 whose temperature was adjusted to 5 ° C. in another container was quickly added so that the isocyanate index was 110. After stirring for 3 seconds at 6000 rpm with a high-speed stirrer, this mixed solution was quickly transferred to a 2 L polyethylene cup whose temperature was adjusted to 22 to 25 ° C. and subjected to foam molding. At this time, the foaming reactivity in a 2 L polyethylene cup was measured. Further, the moldability, foam density and foam odor of the obtained rigid polyurethane foam were evaluated. These results are also shown in Table 2.

なお、発泡反応性、フォームの成形性の評価、フォーム密度の測定、フォーム臭気の判定は以下のとおり実施した。

The foaming reactivity, foam moldability evaluation, foam density measurement, and foam odor determination were carried out as follows.

・ Measurement of foaming reactivity.
Cream time: foaming start time, and the time when the mixed liquid started to foam was measured visually.
Gel time: It was the resin formation time, and the time during which the stringing phenomenon occurred when a thin rod-like object was pushed into the foamed foam and pulled out was measured.
Rise time: The time for the rising of the foam to stop was measured visually.

-Formability of foam.
The moldability was evaluated as follows by observing the appearance of the foam and the state of the cells.
○: The foam surface is smooth and the foam cells are fine.
Δ: Some irregularities are seen on the surface of the foam, but the foam cells are fine.
X: Unevenness is seen on the surface of the foam, and the foam cell is large.

• Measurement of foam density.
The center of the foam foamed in a 2 L polyethylene cup was cut into a size of 6 cm × 6 cm × 10 cm, and the size and weight were accurately measured to calculate the foam density (kg / m ³ ).

-Judgment of foam odor.
The foam cut for foam density measurement was sealed in a polyethylene bag, and three monitors sniffed the inside of the polyethylene bag, and the odor intensity was evaluated in three stages.
○: There is almost no odor from the foam.
Δ: There is a smell from the foam.
X: Strong smell from foam.

  As can be seen from Table 2, in the production examples (Examples 1 to 3) of the spray-type rigid polyurethane foam using the amine carbonate obtained in Preparation Example 1, the liquid temperatures of the premix liquid and the polyisocyanate are Compared to the comparative example in which the addition amount of N, N, N′-trimethylaminoethylethanolamine (trade name: TOYOCAT-RX5), which is an amine catalyst, is the same despite the low temperature of 5 ° C. The cream time that is the foaming start time is fast and the initial foaming property is excellent. That is, Comparative Examples 1 to 3 are examples in which lead amine 2-ethylhexanoate was added without using the amine carbonate obtained in Preparation Example 1, but N, N, N ′ which is an amine catalyst. -Compared to the examples in which the amount of trimethylaminoethylethanolamine added is the same, the cream time is slow, and a large amount of amine catalyst is further required to obtain the same reactivity.

  Moreover, Example 4 is an example using the amine carbonate obtained in Preparation Example 2, but has a quick cream time and excellent initial foamability.

  Examples 5 to 7 are examples in which bismuth neodecanoate, zinc neodecanoate, and quaternary ammonium salt catalyst were used instead of the 2-ethylhexanoic acid potassium salt catalyst. The cream time is fast as in the case of Example 3 to Example 5.

  In Examples 10 to 11, only N, N, N′-trimethylaminoethylethanolamine, which is an amine catalyst, was used as a catalyst, but the cream time, which is the foaming start time, is fast and the initial foaming property is excellent. .

  On the other hand, Comparative Examples 4 to 6 are examples in which N, N, N′-trimethylaminoethylethanolamine is increased in order to increase the cream time, which is equivalent to the example using amine carbonate. A large amount of amine catalyst needs to be added in order to achieve the cream time.

  Moreover, although the comparative example 7 is an example which added only the amine compound instead of the amine carbonate, cream time is late compared with the case where an amine carbonate is used.

  In Comparative Example 8, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (trade name: TOYOCAT-DT, manufactured by Tosoh Corporation) instead of N, N, N′-trimethylaminoethylethanolamine However, the improvement of cream time is insufficient and the odor of the foam is strong.

  Comparative Example 9 is an example using the N-methylethanolamine carbonate obtained in Preparation Example 3, but the improvement in cream time is insufficient as compared with Examples.

  From these results, it can be seen that in the method for producing a spray-type rigid polyurethane foam of the present invention, a rigid polyurethane foam having a fast foaming start time can be produced without polluting the environment.

Example 10, Comparative Example 10 to Comparative Example 11.
<Manufacture of spray type rigid polyurethane foam>
The example which manufactured the spray type rigid polyurethane foam using the amine carbonate obtained by the preparation example 1 is shown. About 15 kg of each of the premixes of Example 10, Comparative Example 10, and Comparative Example 11 were prepared at the raw material mixing ratio shown in Table 3, mixed well, and set in a spray machine. Similarly, after setting the polyisocyanate shown in Table 3 to a spray machine, spray machine foaming was performed under the foaming conditions shown below. The reactivity at the time of foaming was measured with a liquid mixture discharged from a spray gun to a slate plate (30 × 30 cm) adjusted to a surface temperature of 0 ° C. for about 0.5 seconds. For comparison of the core density of the foam and the moldability of the foam, a foam layer having a thickness of about 50 mm was molded on a slate plate (30 × 30 cm) and compared. The results are shown in Table 3.

なお、発泡条件、反応性の測定、フォームの成形性の評価は以下のとおり実施した。

In addition, foaming conditions, reactivity measurement, and foam moldability were evaluated as follows.

-Foaming conditions.
Spray machine: H-2000 manufactured by Gasmer.
Mixing ratio: premix / isocyanate = 1/1 (volume ratio).
Raw material liquid temperature: 40 ± 1 ° C.
Spray substrate: slate plate (30 × 30 cm).
Substrate surface temperature: 0 ° C.

・ Reactivity measurement.
Cream time: The time when the foam starts to rise is measured using a stopwatch.
Rise time: Use a stopwatch to measure the time when the rising of the foam stops.

-Formability of foam.
The appearance of the foam molded on the slate plate was visually observed and evaluated as the moldability as follows.

○: The foam surface is smooth.
△: Some unevenness is seen on the foam surface.
×: Many foams are formed on the surface of the foam.

-Foam core density.
The center part of the foam molded on the slate plate was cut into a size of 200 × 200 × 30 mm, and the core density was calculated by accurately measuring the size and weight.

  Example 10 is a production example of a spray-type rigid polyurethane foam using the amine carbonate obtained in Preparation Example 1. It can be seen that, even in foaming using a spray machine, cream time, which is the foaming start time, is fast and excellent in initial foaming properties. Comparative Example 10 is an example in which 2-ethylhexanoic acid potassium salt and N, N, N′-trimethylaminoethylethanolamine were used as catalysts, but the cream time was slow. Comparative Example 11 is an example of a conventional system using toxic lead 2-ethylhexanoate.

Claims (6)

In a method for producing a spray-type rigid urethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst, a foaming agent, and if necessary, an auxiliary agent, as a part or all of the foaming agent, the following general formula (1)

(In the formula, R _{1 to} R ₄ each independently represents a hydrogen atom or a methyl group. N is an integer of 1 or more.)
Tertiary amines and quaternary ammonium salts using as a catalyst a foaming additive comprising a salt of carbon dioxide and one or more amine compounds selected from the group consisting of amine compounds And one or more catalysts selected from the group consisting of carboxylic acid metal salts (excluding salts of lead, tin, and mercury), and a method for producing a spray-type rigid polyurethane foam. The method for producing a spray-type rigid polyurethane foam according to claim 1, wherein the amine compound represented by the general formula (1) has a molecular weight of 104 or more. Tertiary amines are N, N-dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N′-trimethyl-N ′. -Hydroxyethylbisaminoethyl ether, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N'-methylpiperazine, N, N-dimethylaminohexanol, and The spray-type rigid polyurethane foam according to claim 1 or 2, which is one or more compounds selected from the group consisting of 5-dimethylamino-3-methyl-1-pentanol. Manufacturing method. The quaternary ammonium salt is selected from the group consisting of tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, and tetramethylammonium 2-ethylhexanoate. The manufacturing method of the spray type rigid polyurethane foam in any one of Claims 1 thru | or 3. The spray according to any one of claims 1 to 4, wherein the carboxylic acid metal salt is selected from the group consisting of a bismuth salt of a carboxylic acid, a zinc salt of a carboxylic acid, and an alkali metal salt of a carboxylic acid. Of manufacturing rigid polyurethane foam. The method for producing a spray-type rigid polyurethane foam according to any one of claims 1 to 5, wherein only the foaming additive according to claim 1 and water are used as the foaming agent.