JP2001026629A - Curable composition of polyurethane foam and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition of a polyurethane foam which has an excellent preparation stability and low contents of gas-generating component and bleed-out component, and a preparation process thereof. SOLUTION: A curable composition of a polyurethane foam having low contents of gas-generating component and bleed-out component is prepared using a combination of a reactive amine catalyst (A) having within a molecule at least one hydroxy group or mercapto group which is reactive against polyfunctional isocyanates or an amine catalyst (B) which has an acid dissociation constant pKa of 9 or larger and allows strong gelation or a mixture of these, and a mixture comprising (C) at least one organic metal salt catalyst chosen from the group consisting of (1) a potassium salt or sodium salt of an octylic acid, (2) a naphthenate or octylate of iron (III), nickel or copper having a melting point or softening point of 150 deg.C or higher, (3) an acetylacetonate metal salt of iron (III), nickel or copper and (4) an alkoxy titanium ester compound having a Ti-O-C bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a computer-related device such as a hard disk device or a CD-ROM device.
Alternatively, a curable composition of a polyurethane foam having a low gas generating component suitable for a soundproofing material and a packing material for other electronic devices or a clean room, a method for producing a polyurethane foam from the composition, and the foaming The present invention relates to a soundproofing material and a packing material for a computer-related device using a body, or for other electronic devices or a clean room.

[0002]

2. Description of the Related Art Conventionally, polyurethane foam has been used as a soundproofing material and packing material for computer-related equipment or for other electronic equipment or clean rooms. This polyurethane foam has a polyol component,
It is obtained by reacting a composition containing a polyfunctional isocyanate and a blowing agent in the presence of a catalyst or a catalyst and a foam stabilizer. As a catalyst for producing a polyurethane foam, a metal catalyst composed mainly of a tin-based organic acid and an amine catalyst have been conventionally used alone or in combination, but a tertiary amine compound which is an amine catalyst is particularly preferred. Used in However, conventional amine catalysts have various problems. That is, since the amine catalyst has a low boiling point,
Irritating odors of these compounds occur during the production of the polyurethane foam or even after the product is manufactured. Furthermore, in the products obtained using these compounds, the compounds remaining in the products bleed out and are released as volatile components to the outside air for a long time. For this reason, if it is used as a soundproofing material or a packing material in an automobile cabin, an example of fogging the glass may occur, and it is known that the use of an amine catalyst is not preferable. In addition, in the case of soundproofing materials and packing materials for electronic equipment, the generation of silicone used as a foam stabilizer (Beat-out) causes an important problem,
In some cases, a silicone foam stabilizer cannot be used.

[0003] In order to solve this problem, a compound having a hydroxyl group in the molecule has a very low odor as an amine catalyst for urethane production, and a non-transferable catalyst in a polyurethane resin is disclosed in Japanese Unexamined Patent Publication No. 255120 and the like. However, the present inventors have manufactured a polyurethane foam using a non-migration type catalyst as a single unit, particularly in an application requiring low gas generation with a small amount of gas generated from a foam product (hereinafter simply referred to as gas generation). if you did this,
The following problems have been pointed out. : Since the gelling reaction is slower than the initial foaming reaction, a large amount of catalyst needs to be added. Because the initial foaming reaction is extremely fast, not only is it difficult to apply the undiluted solution uniformly, but also a heterogeneous product with streaks and unevenness in the manufactured polyurethane foam, which greatly impairs the product value. Manufacturing problems occur. Continuous production of relatively thin (50 mm or less) polyurethane foam by traverse method, reverse coater method, or die method causes problems such as gelling of the reaction solution and adhesion to the coating equipment. Production in quantity is essential. For this reason, when the product is in a state where the gelation reaction of the product is insufficient and the rolled product is wound or a single-plate cut and laminated product is manufactured and stored, the products adhere to each other (blocking) and it is difficult to obtain a good product. appear. Further, even if a product which can be produced with a large amount of catalyst added is obtained, the catalyst which could not be non-transferable remains in the product, which is not satisfactory as a reduction in gas generation components.

[0004] When a non-migratory amine catalyst and an organotin-based metal catalyst are used in combination, there are the following advantages. Due to the effect of the combined use of the catalyst, the amount of the non-transferred catalyst can be significantly reduced. By adjusting the amount of the catalyst added, the balance between the initial foaming reaction and the gelling reaction can be easily measured. In the manufactured product, the gelling reaction is increasing and the problem of blocking can be solved.Thus, although the drawback of the single use of the non-migratory amine catalyst can be improved to some extent by the combined use, the organotin-based catalyst has many problems. Since the compound does not have an active group that reacts with the functional isocyanate, it remains in the product as a transferable catalyst, so that the compound easily bleeds out to the surface of the product. Further, it is considered that the compound may be released from the product as a volatile component to the outside air for a long time in spite of its relatively high molecular weight. Therefore, when used as a soundproofing material or packing material for electronic equipment, the organometallic catalyst easily bleeds out or vaporizes on the product surface, and contaminates the parts during the work to be incorporated into the electronic equipment or the parts. In some cases, defective contacts and erroneous operations may occur. Recently, polyurethane foams have been used as soundproofing materials for stepping motors and light receiving devices for laser printers. Polyurethane foam is also used as a gasket material for hard disk drives.
It is particularly problematic because silicone foam stabilizers and organotin catalysts can cause abnormal reading of media. Furthermore, as the storage capacity increases year by year, the temperature inside the device has increased from about 70 to 100 ° C. or more, and the gas generation at high temperatures has been regarded as a problem.

[0005] As a countermeasure, a method of thermally baking or the like to thermally decompose the compound bleeding out to the product surface and forcibly removing the compound or a method of washing can be considered. In the former heat treatment, the treatment temperature is set to a high temperature. Since the processing time is long, there is a problem that the product is thermally deteriorated. It is considered that it is technically very difficult to completely remove it. Even with the latter cleaning method, it is technically difficult to clean the inside of the product, which is a low-permeability packing material, even if the product surface can be cleaned. Even if the processing can be performed as described above, it is expected that a long processing time will be spent and the process will be complicated, so that it is not very realistic considering practicality.

[0006]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that either a reactive amine catalyst or an amine catalyst having strong gelation,
Alternatively, by using these mixtures in combination with one or more selected from specific organometallic catalysts, the amount of catalyst added can be made extremely small, and the gas generation component and bleed-out component can be extremely low. The inventors have found that a curable composition of a suppressed polyurethane foam is obtained, and have completed the present invention.The object of the present invention is to generate gas by using a specific amine catalyst and a specific organometallic catalyst in combination. To provide a curable composition of a polyurethane foam in which the components and the bleed-out component are extremely low, and to provide a soundproofing material and a packing material for a hard disk device comprising a polyurethane foam using the curable composition. It is to be.

[0007]

SUMMARY OF THE INVENTION The gist of the present invention is to provide a polyurethane foam obtained by reacting a composition containing a polyol component and a polyfunctional isocyanate in the presence of a catalyst. Either a reactive amine catalyst (A) having at least one hydroxy group or mercapto group in the molecule which reacts with the functional isocyanate or an amine catalyst (B) having an acid dissociation constant pKa of 9 or more and having a strong gelation On the other hand, or a mixture thereof, and potassium or sodium salt of octylic acid, naphthenic acid or octylate of iron (III), nickel, copper having a melting point or softening point of 150 ° C. or more, iron (III), nickel, acetyl of copper At least one organic gold selected from the group consisting of an acetonate metal salt and an alkoxy titanium ester compound having a Ti-OC bond A curable composition of generated gas components and bleed-out components suppressed low polyurethane foam, which comprises in combination with using a mixture of the catalyst (C). That is, the curable composition of the polyurethane foam in the present invention is an important factor that affects the production stability and the gas generation component, and does not use a reactive amine catalyst or a tin-based organometallic catalyst. By using one of the amine catalysts having strong gelling or a mixture thereof and a mixture selected from one or more of the specific organometallic catalysts, an extremely small amount of the catalyst is added. Thus, it was possible to provide a curable composition of a polyurethane foam in which the gas generation component and the bleed-out component were kept low, and a method for producing the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a curable composition of a polyurethane foam according to the present invention, in which a gas generating component and a bleed-out component are suppressed to a low level, will be specifically described. In the present invention, by using a reactive amine catalyst, it is taken into the urethane resin and becomes a non-migrating type, whereby bleed out to the product surface and gas generation components can be suppressed low.
In the production of foams, considering that the initial foaming reaction is slow and the gelation reaction is fast, a compound having a hydroxy group and a mercapto group is preferable as the reactive group. However, in the use of only these, gelling is delayed when the number of added parts is adjusted to satisfy the initial foaming reaction,
Conversely, if the addition amount is large enough to satisfy the gelling reaction, the initial foaming reaction is fast, so it is difficult not only to apply the reaction stock solution uniformly, but also to the produced polyurethane foam, streaks and unevenness occurred. Non-homogeneous products, resulting in significant loss of product value, unreacted catalysts remaining, reducing outgassing components due to long-term continuous production such as gelling of reaction stock solution and adhesion to coating equipment There are problems such as inability to do so, which does not satisfy the object of the present invention.

The present inventors have found that the use of a combination of the above-mentioned reactive amine catalyst and an amine catalyst having an acid dissociation constant pka of 9 or more and a strong gelation allows the initial foaming reaction / gelation reaction with a small amount of catalyst to be added. And found that the gas generation component can be reduced, and obtained a preliminary result, and filed a separate application. The acid dissociation constant pka is generally used as a guide to indicate the strength of the gelation reaction of an amine catalyst. It is considered that the larger the numerical value, the higher the gelation reaction. Acid dissociation constant pk
a is an automatic potentiometric dropping device (A manufactured by Kyoto Electronics Industry Co., Ltd.)
T-3I0J), the purified water mixed solution adjusted to 0.1 molar equivalent of the amine catalyst was titrated with 0.1 molar hydrochloric acid to determine the pH at the half equivalent point, and this was adopted as the pka value. The measurement was performed at 25 ° C. However, a catalyst having a strong gelation remains in the urethane resin in a trace amount as a migratory component, and is not sufficiently satisfied to reduce the target gas generation component and the outgas component in the present invention. When the amount of addition is reduced in the combined use system with the amine catalyst (A), the curing reaction of the urethane resin is significantly delayed. It has been found that there is a problem such as adhesion between products (blocking), resulting in a lack of manufacturing stability. As a result of intensive studies to solve this problem, one of the reactive amine catalyst (A) and the amine catalyst (B) having strong gelling, or one of these compounds and a specific organometallic catalyst, By using a mixture selected from two or more in combination,
This makes it possible to reduce the outgassing component and the bleedout component.

That is, in the present invention, a reactive amine catalyst (A) which is a tertiary amine compound represented by the following general formula:
And an amine catalyst (B) having an acid dissociation constant pka of 9 or more and strong gelation having 2 to 10 carbon-carbon bonds in the bond between a nitrogen atom and a hydroxy group, or a mixture of both; It is preferable to use the metal catalyst (C) in combination.

Embedded image (Wherein, R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10)

In the polyurethane foam according to the present invention, a polyurethane foam obtained by reacting a composition containing a polyol component and a polyfunctional isocyanate in the presence of a catalyst has a relatively small thickness (50 mm or less). The polyurethane foam is produced by applying a reaction raw material by a traverse method, a reverse coater method, or a die method, and is continuously produced. Further, the polyurethane foam is produced by ordinary molding, small-quantity casting, or transfer molding. When the above-mentioned thin foam is continuously produced, if the initial foaming reaction / gelling reaction is insufficiently prepared, the application of the reaction raw materials becomes non-uniform, and the coating device is gelled and solidified, so that it is manufactured for a long time. In addition, there is a problem in that when the foamed product is rolled up and the product is cut into a single plate and the laminated product is stored, the products adhere to each other. In particular, in the small-quantity casting method, continuous casting is performed for a long time without washing the casting head, so that there is a problem that the casting head is gelled and solidified.
In the present invention, a reactive amine catalyst (A) and / or an amine catalyst (B) having an acid dissociation constant pka of 9 or more and having high gelation and a specific metal catalyst (C) are used in combination. That is, the curable composition of the polyurethane foam of the present invention has made it possible to suppress the production stability and the gas generation component and the bleed-out component to a low level.

In the above general formula (1), the number of carbon-carbon bonds is an integer of 2 to 10. When the number of carbons is 2 or less, the initial foaming reaction is stronger than the gelling reaction, and the number is 2 or more. In addition, since the initial foaming reaction is weakened and the gelling reaction is strengthened, uniform application of the reaction raw material is facilitated, and if the number exceeds 10, the initial foaming reaction is weak and it is difficult to form fine cells (bubbles). Further, a compound in which a nitrogen atom or an oxygen atom is not interposed between the hydroxy group and the carbon-carbon bond is preferable, and a reactive tertiary amine compound having six carbon atoms is particularly preferable. Although the reason is not clear, it is considered that as the carbon number increases, the affinity with the polyol increases, and the affinity with water decreases, thereby delaying the initial foaming reaction and increasing the gelling reaction. Further, it is considered that a compound in which a nitrogen atom or an oxygen atom is interposed between the hydroxy group and the carbon-carbon bond has an increased affinity for water and hence an initial foaming reaction.

In the present invention, the reactive amine catalyst (A) having a reactive group that reacts with the polyfunctional isocyanate is a tertiary amine compound having at least one hydroxy group or mercapto group in a molecule. Specifically, as the compound having a hydroxy group, N, N-dimethylethanolamine (DMEA), N, N-dimethylethoxyethanol, N, N-dimethylethoxyethoxyethanol, N, N-dimethylaminohexanol,
N, N, N'-trimethylaminoethylethanolamine, N, N, N'-trimethylaminopropylethanolamine, N-methyl-N'-hydroxyethylpiperazine (MHEP), N, N, N'N'- Compounds having a mercapto group, such as teramethylhydroxypropyldiamine (TMHPDA), include triazinethiol triazine-trithiol, butylaminotriazine-dithiol, hexylaminotriazine, hexylaminotriazine-dithiol, diethylaminotriazine-dithiol, butoxyaminotriazine. And imidazole-based 1-methyl-5-mercapto-1,2,3,4 tetrazole and the like, and mixtures thereof.

In the present invention, the amine catalyst (B) having a strong gelation when used as a mixture with the reactive amine catalyst (A) may be an imidazole-based or cyclic triazine-based compound having an acid dissociation constant pka of 9 or more. By selecting from cyclic amidine-based compounds, the gelation reaction is stronger than the initial foaming reaction, so it is possible not only to increase the gelation reaction with a small amount of addition, but also to have a synergistic effect when used in combination with a reactive amine catalyst. Is exhibited, so that the amount of catalyst to be added is extremely small. For example, if a tertiary amine catalyst having a pka of less than 9 is selected, the initial foaming reaction is stronger than the gelling reaction, which may cause a problem in uniform application of the reaction raw materials when producing a polyurethane foam, or enhance gelation. Therefore, a large amount of catalyst is required, so that a large amount of transferable catalyst remains in the urethane resin, so that it is difficult to reduce it as a gas generating component.

Specifically, as the amine catalyst (B) having an acid dissociation constant pka of 9 or more and having a strong gelation, imidazole compounds such as 1-methyl-5-mercapto-1,2,3,4
Tetrazole, 2-methylimidazole, 2-ethyl-
4-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2methylimidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, etc., dimethylcyclohexylamine
(DMCHA), dimethylbenzylamine (DMBA), dicyclohexylamine or organic acid salts, and the like, and mixtures thereof. These amine compounds are used as one kind or a mixture of two or more kinds, and are not limited thereto.

The highly gelling amine catalyst (B) is preferably a tertiary amine compound having a boiling point of 180 ° C. or lower, and is preferably a triazine tertiary amine catalyst. That is, dimethylcyclohexylamine (DMCHA-159 ° C), dimethylbenzylamine (DMBA-163 ° C), and tris-dimethylaminopropyl-hexahydro-S, which are tertiary amine compounds having an acid dissociation constant of 9 or more and a boiling point of 180 ° C or less. -Triazine (141 ° C), etc.
It has been found that by selecting from these and mixtures thereof, the gas generating component is reduced. By selecting a tertiary amine catalyst having a boiling point of 180 ° C. or less for the highly gelling amine catalyst (B) to be used as a mixture with the reactive amine catalyst (A), the strongly gelling amine catalyst (B) can be used for foam production. Since it easily vaporizes due to heat generation and after-cure, the amount of transferable amine catalyst remaining in the product is reduced, so that it is possible to obtain a polyurethane foam with a low gas generating component. . In addition, since the amount of the transferable amine catalyst remaining in the product is reduced, the amount of the dissociation catalyst that accelerates the decomposition of the product due to thermal degradation is reduced, so that the polyurethane foam has the characteristic of improving the heat resistance. Things.

The highly gelling amine catalyst (B) used in the present invention is, in particular, a tris-dimethylaminopropyl-hexahydro-S-triazine which is a cyclic tertiary amine catalyst having a boiling point of 150 ° C. or less. Alternatively, they have found that a polyurethane foam having a low outgassing component can be obtained by specifying and using an organic acid salt thereof.

The present invention relates to the above reactive amine catalyst (A)
It is a curable composition of a polyurethane foam which is used in combination with one of an amine catalyst (B) having strong gelation, or a mixture thereof and an organic metal salt catalyst (C). Examples of the organometallic catalyst (C) include potassium or sodium octylate, iron (II) having a melting point and a softening point of 150 ° C. or more.
I), nickel, copper octylic or naphthenic acid compounds,
It is at least one selected from the group consisting of iron (III), nickel, copper acetylacetonate metal salts of copper, and alkoxy titanium ester compounds having a Ti-OC bond.

In the present invention, potassium or sodium salt of octylic acid is used as the amine catalyst (either a reactive amine catalyst (A) or an amine catalyst having strong gelling (B), or a mixture thereof). When a monovalent alkali metal salt of potassium or sodium octylic acid is used in combination, a synergistic effect is exhibited, and the initial foaming reaction / gelation of the urethane foam can be easily performed with a small amount of catalyst. It has been found that the bleed-out component and the gas-evolving component can be kept low even though an unreacted organometallic catalyst is used, but the reason is not clear.

Iron (II) having a melting point and a softening point of 150 ° C. or more
Examples of the compound which is octylic acid or naphthenic acid of I), nickel and copper include powders of iron octylate, nickel octylate, copper octylate, iron naphthenate, nickel naphthenate and copper naphthenate. In the present invention, when the amine catalyst and the specific organometallic catalyst (C) having a melting point and a softening point of 150 ° C. or more are used in combination, a synergistic effect is exhibited, and the initial foaming reaction of the urethane foam with a small amount of catalyst added. / Since the gelling can be easily adjusted and the organometallic catalyst having a melting point and softening point of 150 ° C or higher is used, the resulting urethane foam is solid and finely dispersed, making it difficult to bleed out. Further, it is possible to suppress the bleed-out component and the gas generating component to a low level because they are hardly vaporized as volatile components even when exposed to high temperature conditions.

The acetylacetonate (2,4-pentanedione) metal salt of iron (III), nickel or copper is a compound represented by the following general formula.

[0022]

Embedded image (In the formula, n is an integer of 1 to 4, and M represents a metal.)

Specifically, iron triacetylacetonate {Fe (0C ₃ H ₇ ) ₃ }, diacetylacetonate nickel dihydrate, which is a compound which is solid at ordinary temperature and has a melting point of 150 ° C. or more Ni (OC ₅ H ₇ ) ₂ (H
₂ O) ₂ }, copper diacetylacetonate {Cu (OC)
₅ H ₇ ) ₂ }. These compounds undergo an alcoholophoresis reaction with an alcohol having a carbon number different from that of the bonded alkyl group, causing substitution of the alkyl group, or hydrolysis or a decomposition reaction at a temperature higher than the melting point, releasing acetylacetonate, and finally a metal oxide. Is known to be. In the present invention, the amine catalyst and the melting point are 150 ° C.
When the iron (III), nickel and copper acetylacetonate metal salts having the above are used in combination, a synergistic effect is exhibited,
The initial foaming reaction / gelation of the urethane foam can be easily adjusted with a small amount of catalyst added, and the urethane foam obtained is incorporated into the resin by a chemical bond and becomes a non-migrating type,
Even if the catalytic activity remains, the melting point is as high as 150 ° C. or higher, so that it is solid and finely dispersed and hardly bleeds out. Furthermore, it is hard to vaporize as a volatile component even when exposed to high temperature conditions. It has been found that the bleed-out component and the gas generation component have characteristics and can be suppressed low.

Examples of the alkoxy titanium ester compound having a Ti—O—C bond include tetra-i-propyl titanate {TPT; Ti (OC ₃ H ₇ ) ₄ } and tetra-n-butyl titanate {TBT; Ti (OC
₄ H _{9) 4},} tetrastearyl titanate {Ti (OC
₁₇ H _{35) 4},} triethanolamine titanate {Ti
(OC ₃ H ₇ ) ₂ (OCH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ )
₂ }, titanium lactate {Ti (OH) ₂ (OCH
(CH ₃ ) COOH) ₂ , titanium acetylacetate @ Ti (OC ₃ H ₇ ) ₂ (OC (CH ₃ ): CHCOCH
₃ ) ₂ }, titanium ethyl acetylacetate {Ti
(OC ₃ H ₇ ) ₂ (OC (CH ₃ ): CHCOC ₂ H ₅ ) ₂ }
And the like.

These compounds generally react very sensitively to water to cause hydrolysis, and as a result, an alkoxy group is released to release free alcohol to dimerize, and finally, titanium oxide or titanium oxide water It is known that alcohol is substituted with an alcohol having a carbon number different from that of the bonded alkyl group, and the alkyl group is substituted. In particular, TPT and TBT are compounds that are easily hydrolyzed when exposed to moisture in the air. In the present invention, when an amine catalyst and an alkoxytitanium ester compound are used in combination, a synergistic effect is exhibited, and the initial foaming reaction / gelation of the urethane foam can be easily adjusted with a small amount of catalyst added. Incorporation into the urethane resin by the substitution reaction of the alkyl group during the curing reaction to make it non-migratory, or bleeding out because it disperses finely as a metal compound that releases acetylacetone and does not emit gas, and under high temperature conditions They have a feature that they do not evaporate as volatile components even when exposed, and they have found that the bleed-out component and the gas generation component can be suppressed to a low level.

Among the above compounds, in the present invention, N, N-dimethylaminohexanol, which is a reactive amine catalyst having one hydroxy group in the molecule, or a highly gelling DBU organic acid salt, tris-dimethylamino Propyl-hexahydro-S-triazine, or a mixture thereof with an iron (III) or nickel acetylacetonate metal salt and an alkoxy titanium ester-based metal salt catalyst having a butoxy group and an acetylacetonate group. It is preferably used.

The polyurethane foam of the present invention having a low gas generating component and a low bleed-out component is suitable for use as a soundproofing material and a packing material for a hard disk drive. For packing materials for hard disks, polyurethane foams without using an organic silicone foam stabilizer are desired. In order to produce these foams, it is essential to select a catalyst having particularly strong gelation. This is because, in a curable composition having a slow gelation, bubbles easily merge and become coarse cells, so that it is difficult to obtain a foam having low air permeability with fine cells. As a measure for this, DBU {1,8-diazabicyclo (5,4,0) undecene-7} and DBN {1,5-diazabicyclo (4,3,0) -nonene having a cyclic amidine structure having a pka of about 11 or more -5｝, DBA
By selecting these compounds which are {6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7} or an organic acid salt, there is no catalytic activity at around room temperature and the polyurethane foam The acid is dissociated in the vicinity of 40 to 100 ° C. due to the heat of curing reaction or external heating, and the catalytic activity sharply increases, which has a delay effect of terminating the curing reaction in a short time. A strong amine catalyst. These compounds exhibit an effect when added in a small amount, and are characterized in that the amount of the migrating catalyst remaining in the product can be reduced. Further, tris-dimethylaminopropyl-hexahydro-S-triazine or an organic acid salt of an aminotriazine compound is preferably used, but the above-mentioned strong gelling catalyst remains as a migrating component in the urethane foam. When used in a mixture with a reactive amine catalyst, care must be taken to keep the addition amount to a minimum.

Curability of polyurethane foam using either the reactive amine catalyst (A) or the highly gelling amine catalyst (B), or a mixture thereof and an organometallic salt catalyst (C) The addition amount of the reactive amine catalyst (A) and the strongly gelling amine catalyst (B) in the composition may be 5 to 5 to 4: 1 by weight or 100 parts by weight of the polyol with only the reactive amine catalyst (A). It is desirable to adjust the amount to a small amount of 0.5 part or less, preferably 0.3 part or less, and in the present invention, a reactive tertiary amine having one hydroxy group in the molecule; N, N- Dimethylaminohexanol or a strongly gelling DBU organic acid salt,
Tris-dimethylaminopropyl-hexahydro-S-
It is preferably used in a combination system of any one of triazines, or a mixture thereof with an iron (III) or nickel acetylacetonate metal salt and an alkoxytitanium ester-based metal catalyst having a butoxy group and an acetylacetonate group.

On the other hand, among the organometallic catalysts (C) used in the present invention, alkoxytitanium ester compounds, especially compounds having a butoxy group and an acetylacetonate group, have an appropriate hydrolyzability. When this is specified and used, storage and handling in the urethane foam production process are facilitated, and stable production is possible. Specifically, in the production process of the urethane foam, the catalyst is used after being diluted with another liquid material in advance because it is added in a small amount. However, the organometallic catalyst (C) is liable to undergo hydrolysis. If it is a product, the catalytic activity will weaken over time and storage stability will be lacking, so products of stable quality cannot be obtained, and sufficient care must be taken in storage and handling of raw materials themselves, making the manufacturing process complicated. A problem arises.

In the present invention, the polyurethane foam obtained from the above-mentioned curable composition of polyurethane foam comprises:
By carrying out the heating and baking treatment, the transferable amine catalyst remaining in the product can be easily removed, and a polyurethane foam having a very low gas-evolving component can be obtained. The heating baking treatment of the present invention is desirably performed under conditions in which the polyurethane foam hardly undergoes thermal deterioration,
For example, at 100 to 150 ° C. for 1 to 5 hours, preferably 12
The heating is performed at 0 ° C. or lower for 1 to 5 hours, but it is preferable to perform the vacuum heating baking because the processing can be efficiently performed at a relatively low temperature and in a short time. Particularly, the highly gelling amine catalyst (B) remaining as a transfer type in the product has a boiling point of 180
By specifying and using a compound having a temperature of not more than ° C., there is a feature that it can be easily removed by a heating baking treatment for a relatively short time.
Furthermore, they have found that it is particularly preferable to specify a compound having a boiling point of 150 ° C. or lower. Measurement of boiling point is J
This is the temperature at which the equilibrium reflux rate measured according to IS K 2233-1984 is maintained.

In the present invention, the polyurethane foam obtained from the above-mentioned curable composition of polyurethane foam is:
It uses no organometallic catalyst at all, has low outgassing components and bleed-out components, and can be used as a soundproofing material and packing material for hard disk drives by performing heat baking. Is what you do.

The polyurethane foam curable composition of the present invention can be used in the presence of the above-mentioned amine catalyst and a specific organometallic catalyst in the presence of a polyol component and a polyfunctional isocyanate generally used in the production of a polyurethane foam. The additives are not particularly limited as long as they are used as needed. As polyether polyols, ethylene glycol, glycerin, polyhydric alcohols such as trimethylolpropane, ethylene oxide, propylene oxide, butylene oxide, addition polymerization products obtained by addition polymerization of alkylene oxides such as styrene oxide to these polyhydric alcohols, And mixtures thereof, but are not limited thereto. Polyester polyols include condensates obtained from the condensation reaction of polyhydric carboxylic acids such as adipic acid, phthalic acid, and succinic acid with polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, and trimethylolpropane. And mixtures thereof, but are not limited thereto. Examples of the polymer polyol include, in at least one of the polyols listed above, acrylonitrile in the presence of a radical initiator, a polymer obtained by polymerizing a vinyl monomer such as styrene, and the like, and a mixture thereof. It is not limited to this.

Other polyols include polyols containing melamine or ammonium polyphosphate dispersed therein and phosphorus-containing polyols, polylactone-based polyols obtained by ring-opening polymerization of lactones using polyhydric alcohols, polycarbonate polyols, polygen-based polyols and the like. And mixtures thereof, but are not limited thereto. Further, the polyol is used as an OH group-terminated prepolymer reacted with a polyfunctional isocyanate described below, but is not limited thereto. In particular, for use as a sound absorbing material for automobiles and the like that require low gas generation and low water absorption (water repellency), the use of the following hydrophobic polyol is preferable because water resistance is imparted. The hydrophobic polyol is one that passes a polyol compatibility test described below. Specifically, as dimer acid-based polyols, esterified products of dimer acid and polyfunctional hydroxides such as ethylene glycol, diethylene glycol, trimethylolpropane, and glycerin, castor oil and castor oil modified products, polybutadiene-based polyols and hydrogenated products thereof Products, polyisoprene-based polyols and hydrogenated products thereof. These polyols are OH-terminated prepolymers previously reacted with a polyfunctional isocyanate described below or NCO.
Examples include, but are not limited to, those used as group ends.

The method for testing the compatibility of a polyol is that a sample of 2 g is placed in a glass test tube having a diameter of about 18 mm and a length of 180 mm.
Was weighed, and a solution in which isopropyl alcohol and distilled water were adjusted to a weight ratio of 75 to 25 in advance was dropped by a burette, and the solution gradually became turbid, and 0.5 m was passed through the test tube.
A sample having a solution addition amount of 2 g or less when the line m becomes invisible is judged to be acceptable. This test is performed at a liquid temperature of 25 ° C. Examples of the polyfunctional isocyanate include an aromatic polyisocyanate and an aliphatic polyisocyanate having two or more isocyanate groups in a molecule or a modified product thereof, and specifically, toluene diisocyanate ( TDI), diphenylmethane isocyanate (MDI), isophorone diisocyanate (IPDA)
I), hexamethylene diisocyanate (HDI), tetramethylxylylene diisocyanate (TMXDI)
And mixtures thereof. Or an NCO group-terminated prepolymer reacted with the polyol,
And mixtures thereof, but are not limited thereto.

Examples of the foam stabilizer include an organosilicone foam stabilizer, a surfactant and the like, and a mixture thereof. In the former, it is preferable not to use it depending on the use. It is preferable to use a silicone foam stabilizer having an active group such as a hydroxy group, a mercapto group, an amino group, an epoxy group, and a carboxyl group that reacts with the isocyanate, because the silicone foam becomes non-migratory. The latter includes, but is not limited to, diethylaminooleate, sorbitan monostearate, glycerin monooleate, vinylpyrrolidone, fluorine, organic compounds, and the like, and mixtures thereof. In particular, in the application as a packing material for a hard disk drive which requires low gas generation, the above compound is used with a minimal addition amount, but it is particularly preferably not used. As the foaming agent, for example, water; gaseous nitrogen at normal pressure;
Inert gases such as carbon dioxide gas and air; halogenated alkanes such as monofluorotrichloromethane and dichloride methane; low-boiling alkanes such as butane and pentane; azobisisobutylnitrile that generates decomposed nitrogen gas and the like; Mixtures include, but are not limited to. As other additives, a crosslinking agent, a colorant, a resin modifier, a flame retardant, an ultraviolet absorber, a durability improver, and the like can be optionally used as needed. The curable composition of the polyurethane foam of the present invention uses the above-mentioned various raw materials to form a polyurethane foam, and the production method thereof is conventionally known (1) prepolymer method, (2) ) It can be produced by any one of the one-shot method and the (3) partial prepolymer method. These products include slabs, molds or double-sided skins, as well as small cast molds.

[0036]

Examples and Comparative Examples Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts and percentages are by weight. In addition, the curable composition of the polyurethane foam, conventionally known foaming agents, crosslinking agents, coloring agents, foam stabilizers, resin modifiers, flame retardants, ultraviolet absorbers, additives such as durability improvers, It can be added within a range that does not impair the purpose of the present invention. Next, the production of the foam obtained from the curable composition of the polyurethane foam in Examples and Comparative Examples is carried out by mixing and stirring a compound comprising a polyol, an isocyanate, a catalyst, and other additives. At room temperature
A method of obtaining a foam by free foaming with a liter poly beaker, or after evenly applying the release treatment surface of the process paper subjected to the release treatment using an application bar, covering the process paper so that the release treatment surface also comes to the upper surface, Heating oven (70 ℃ × 3min + 1
(20 ° C. × 4 minutes) to obtain a sheet-like foam by foaming and curing.

The catalysts used in the examples are as follows. Catalyst A: dimethylaminohexanol (Kaorizer No. 25; manufactured by Kao Corporation), reactive amine catalyst having a terminal hydroxy group pKa10 Catalyst B: Tris-dimethylpropyl-hydroxy-S-
Triazine, boiling point 141 ° C. (Kaorizer No. 1
4; Kao Corporation) pKa9.3 Catalyst C: a mixture of bis (dimethylaminoethyl) ether / dipropylene glycol (3 to 7 weight ratio), boiling point 1
70 ° C (Kaorizer No. 12; manufactured by Kao Corporation)
Ka8.8 catalyst D; a mixture of triethylenediamine / dipropylene glycol (1: 2 weight ratio), boiling point 174 ° C (33-L
V; manufactured by Sankyo Air Products Co., Ltd.) pKa8.7 Catalyst E; Potassium octylate Catalyst F; Iron octylate Catalyst G; Iron trisacetylacetonate (powder) Catalyst H; Titanium acetylacetonate (alkoxy titanium ester compound) Catalyst I; DBU [1,8-diazabicyclo (5,4,
0) -undecene-7] octylate, boiling point 240 ° C.
(Sa.102; manufactured by Sun Apro Co., Ltd.) pKa11.5 Catalyst J; Diacetylacetonate nickel dihydrate (powder) Catalyst K: Dibutyltin dilaurate

Examples 1 to 6 and Comparative Examples 1 to 4 100 parts of polyol having an OH value of 40 by adding propylene oxide and ethylene oxide to glycerin / ethylene glycol (Actocol GS-92; manufactured by Takeda Pharmaceutical Co., Ltd.) 2.5 parts of purified water as a foaming agent, 3 parts of a carbon black colorant (TUR-0235; manufactured by Toyo Ink Mfg. Co., Ltd.), a predetermined amount of a catalyst, and a silicone foam stabilizer 0.1 having a terminal OH group. Part, NPC prepolymer NCO 23% using diphenylmethane diisocyanate
(Takenate SI-45P; manufactured by Takeda Pharmaceutical Co., Ltd.) and crude diphenylmethane diisocyanate NCO 31%
(Takenate ISO-01P; manufactured by Takeda Pharmaceutical Co., Ltd.)
Of the 8/2 weight blend of Ind at the NCO / OH equivalent ratio of Ind
The mixture ex103 was mixed and stirred at a raw material temperature of 25 ° C., and a free foaming method was performed to produce a polyurethane foam having an expansion ratio of about 20 to 25 times. In addition, regarding the curing reaction of polyurethane foam, the initial evaluation of the foaming reaction as a cream time (cream) and the gelation reaction as a tack free time (tack free) are performed as a curing reaction evaluation. This is to easily evaluate the adhesion (locking) between products that occurs during the uniform application and curing of the application device, winding of a roll-shaped product or lamination and storage of single-plate cut products. A cream is a compound that starts stirring. The term “tack” means the time from the end of contact with the surface skin of the foam after the completion of the curing reaction and the elimination of stringing and tack. Further, a test piece was collected from the obtained foam, and the density (g / cm ³ ) was measured according to JIS K6401.

Quantitative analysis of outgassing components is performed according to JIS K0
The measurement was performed according to 123 gas chromatograph mass spectrometry (GC-MS). The GC-MC analyzer is a QP- made by Shimadzu Corporation.
5000, headspace sampler is JHS-100 / AQ-200 manufactured by Nippon Kagaku Kogyo, column is DB-1
(0.25 mm × 30 m, 0.25 μm), and as an analysis operation, about 0.4 g of a sample cut into a width and height of about 3 mm × length of about 2 cm or less was collected in a test tube, and subjected to heat extraction conditions; At 150 ° C. × 10 minutes, at a heating rate of 10 ° C./min,
Gas analysis was performed by the purge and trap method, and quantitative determination was performed based on the peak area of the amine component. Based on the results, evaluation was performed according to the following evaluation criteria. For quantification, a trimer of dimethylsiloxane having a known concentration is used as a standard solution. Table 1 shows these results.
It is shown in FIG.

[0040]

[Table 1]

[0041]

[Table 2]

In Examples 1-4, a reactive amine catalyst having a hydroxy group and various organometallic salt catalysts were used in combination, and the balance of the initial foaming reaction / gelation reaction was reduced with a small amount of added catalyst. It can be seen that the curable composition was removed. Example 5 shows a case where the amine catalyst in Example 4 was a mixture of a reactive amine catalyst having a hydroxy group and an amine catalyst having an acid dissociation constant pka of 9 or more and strong gelation, and was added in a small amount. It can be seen that the composition is a curable composition with a small amount of gas-evolving components and a well-balanced reaction.

Comparative Example 1 used only a reactive amine catalyst having a hydroxy group. When the amount added was such that the gelation reaction was satisfactory, the initial foaming reaction was too early.
In Comparative Examples 4 to 3, the initial foaming reaction was too fast and the gelling reaction was insufficient. In Comparative Example 4, a small amount of reactive amine catalyst and a strong gelling amine catalyst were added in order to reduce gas generation components. The gelation reaction was insufficient. All of them have a large amount of gas generating components, and the balance between the desired foaming reaction and the gelling reaction is poor, so that the present invention cannot be satisfied. Example 6 uses a hydrophobic polyol having an OH value of 70 obtained by addition polymerization of dimer acid and short-chain diol and triol in the catalyst system of Example 3.

A sample was taken from the obtained foam, immersed at a depth of 10 cm for 24 hours in a state where the sample was compressed at 50%, taken out, the volume of water absorbed by the sample was measured, and the water absorption (vol. %). As a result, the water absorption of Example 3 was 8%, while the water absorption of Example 6 was 3%.
%, Which indicates that the foam has improved water resistance, and is suitable as a sound-absorbing material for automobiles and the like that require low gas-generating properties and low water-absorbing (water-repellent) properties.

Examples 7 to 12 and Comparative Examples 5 to 7 Except that the amine catalyst was changed, foaming was carried out by mixing and stirring the composition at the raw material temperature of 25 ° C. to obtain a sheet-like foam. A polyurethane foam having an expansion ratio of about 20 to 25 was prepared. As for the curing reaction of the polyurethane foam, the initial foaming reaction is evaluated in the coating state, and the gelling reaction is evaluated for the blocking property, so that the problems in the production of the foam can be easily evaluated in the same manner as in the slab foaming method. The reaction material mixed and agitated using a coating bar is used to evaluate the ease of application to the release-treated surface of the process paper and the uniformity of the thickness of the obtained foam. Is obtained by dividing the foam immediately after the completion of the curing reaction, laminating the foam, and then peeling it after 4 hours or more to evaluate the degree of peeling. Evaluation criteria for coating state Evaluation criteria for blocking properties ○: Foam of uniform application, uniform thickness ○: Easily peeled, no skin damage △: Foam of non-uniform thickness, non-uniform application △: Heavy peeling but skin damage None ×: Foaming reaction could not be applied quickly ×: Peeling was heavy and skin damage was generated. These results are shown in Table 3.

[0046]

[Table 3]

In Examples 7 to 10, the reactive amine catalyst having a hydroxy group was used in combination with various organometallic salt catalysts of the present invention. In Examples 11 to 12, the reactive amine catalyst of Example 10 was used. It can be seen that the curable composition was added in a small amount as a mixture of an amine catalyst having strong gelation, and the outgassing component in which the initial foaming reaction / gelation reaction was balanced was as small as 50 or less. Comparative Examples 5 to 7 used a reactive amine catalyst and an amine catalyst having an acid dissociation constant pka of 9 or less in combination. A small amount of a reactive amine catalyst and a strong gelling amine catalyst are used in combination, and the gelling reaction is good. In each case, the amount of gas generating components is large, and the present invention cannot be satisfied.

Examples 13 to 19 and Comparative Examples 8 to 10 30 parts of a polyol having an OH value of 56 as an adduct of propylene oxide and ethylene oxide to glycerin, 70 parts of a polyol having an OH value of 56 as an adduct of glycerin and propylene oxide, 4 parts of a trifunctional crosslinking agent having a value of 910,
1,4 butanediol 4 parts, non-silicone foam stabilizer 0.1
Parts, 0.3 parts of purified water as a foaming agent, 15 inorganic fillers
Parts, 3 parts of a carbon black colorant, a predetermined amount of a catalyst, 29% NCO in a carbodiimide-modified product of diphenylmethane diisocyanate at an NCO / OH ratio of Index 105
The mixture was stirred and mixed at a raw material temperature of 25 ° C. to obtain a sheet-like foam, thereby producing a sheet-like polyurethane foam having an expansion ratio of about 3 times. As for the curing reaction of the polyurethane foam, the initial foaming reaction was evaluated in the applied state, and the gelation reaction was evaluated for restorability in the same manner as in the above-described example, and the problems in producing the foam were easily evaluated. I do. Restorability refers to a foam with a flat tip with a diameter of 10 mm immediately after the end of the curing reaction.
The aluminum jig was pressed strongly for 5 seconds, and the restoration rate after 5 seconds from opening was determined by the following formula, and evaluated according to the evaluation criteria.

[0049] Evaluation criteria of restorability ○: Restoration rate of 80% or more △; Restoration rate of 50 to 80% ×; Restoration rate of 50% or less The obtained foam has an air leak performance required for a packing material. The evaluation was made based on sex. The air leaking property refers to a ring-shaped test piece (thickness = outer diameter 36)
mmφ = inner diameter 32 mmφ), and the air leak property is measured using the test device of FIG.

Specifically, a test piece was formed on an acrylic
% After compression, a predetermined pressure (mmAq)
And the amount of air leaking to the outer diameter of the test piece is read by a flow meter (cc / min). For air leaking, a pressure of 1
For every 000 mmAq, increase to 5000 mmAq.
The point at which a leak exceeding 0 cc / min occurred was defined as the air leak pressure, and was evaluated according to the following evaluation criteria. Evaluation criteria of air leak ◎: 5000 mmAq or more ○; 3000 mmAq △; 2000 mmAq ×; 1000 mmAq or less

Further, the obtained foam was subjected to a quantitative analysis of a gas generating component and a quantitative analysis of a bleed-out component by an analytical method to be described later for the presence or absence of a heat baking treatment. The heating and baking treatment performed in the present invention is performed by taking a sample of about 10 cm square in thickness from the obtained foam and suspending it in a hot air circulating oven adjusted to 120 ° C. for 4 hours in a suspended state. The present invention is not limited to this condition, and has such features that if the vacuum heating baking treatment is performed, the treatment temperature can be set low or the treatment effect can be exhibited in a short time.

The quantitative analysis of the bleed-out component was performed using an ESCA analyzer manufactured by JEOL Ltd .;
As an analysis operation, a test substrate (1 cm square made of aluminum) was brought into contact with a sample cut into a thickness of 1 cm square or more, and heated at 100 ° C. for 15 hours in a state where the whole was sealed with aluminum foil.
The components adhering to the test substrate were analyzed by ESCA, and were determined from the peak area (cts-eV / s) of the nitrogen element for the amine catalyst and the metal element for the organometallic catalyst. still,
The detection amount from the test substrate was subtracted from the measured value.
Table 4 shows the results.

[0053]

[Table 4]

Examples 13 to 16 used a reactive amine catalyst having 6 carbon atoms in combination with various organic metal salt catalysts of the present invention, and Example 17 used an amine catalyst in Example 16 in which a hydroxyl group was used. A small amount was added as a mixture of the reactive amine and the highly gelling amine catalyst, and the initial foaming reaction / gelation reaction was balanced. Further, these foams were confirmed to be curable compositions of polyurethane foams in which the gas generating component and the bleed-out component were reduced, satisfying the present invention. In particular, by performing the heating baking treatment, the gas generation component and the bleed-out component are reduced.

Incidentally, as shown in Example 17, although the non-reactive amine catalyst originally has the property of easily remaining as a transferable catalyst in the urethane resin, the amount of the amine catalyst is extremely small due to the synergistic effect with the organometallic catalyst. It is found that the amount of gas generation and bleed-out components can be reduced because the amount of addition can be reduced. In Examples 18 to 19, the reactive amine catalyst was added in a small amount (0.1 part), and the organometallic catalyst was used in combination with an alkoxy titanium ester compound or nickel acetylacetate. Bleed-out components are further reduced. In particular, those using a combination of a reactive amine and the organometallic catalyst of the present invention are preferable because the gas generating component is 30 or less.

Comparative Examples 8 and 9 show that the reactive amine catalyst and pk
a was used in combination with an amine catalyst having an a of 9 or less, but the obtained foam had insufficient reaction, poor resilience and poor air leak properties, and had a gas generating component of 100 even after heating and baking. Above, many, and the bleed-out component is 10
Since it is more than 00, it does not satisfy the present invention. In Comparative Example 10, an amine catalyst having an acid dissociation constant pka of 9 or less was used in combination with an organotin catalyst, and although a good foam was obtained, the gas generating component and the bleed-out component of air and metal were reduced. Many do not satisfy the present invention. As described above, in the present invention, a specific amine catalyst and an organometallic catalyst are used in combination, so that even when exposed to a high temperature condition, the gas-forming component and the bleed-out component are suppressed to a very low level. Since the body is obtained, it is suitable as a soundproofing material and a packing material for a hard disk device.

[0057]

The effects of the present invention are listed below. * When producing a sheet-like polyurethane foam with a relatively small thickness, the initial foaming reaction and the gelling reaction can be easily adjusted with a very small amount of catalyst added, so it is a good product with excellent production stability and no blocking. Can be manufactured. * Since the polyurethane foam of the present invention does not use a silicone-based foam stabilizer and has extremely low outgassing components and bleed-out components, it can be used for soundproofing materials and packing materials for electronic equipment. Contact failure and erroneous operation can be suppressed.
In addition, even when used with soundproofing materials and packing materials for automobile interiors,
The occurrence of fogging that fogs the glass is suppressed. * The polyurethane foam of the present invention has extremely low residual amounts as an amine catalyst and an organometallic catalyst in a catalytically active state, so that durability such as heat resistance is improved. * The polyurethane foam of the present invention can easily remove the transferable amine catalyst remaining in the product by performing the heat baking treatment. * When a tertiary amine catalyst with a boiling point of 180 ° C and strong gelation is selected, a small amount of residual gas in the product is subjected to a relatively short heating baking process, etc., thereby further reducing the gas generating components. A polyurethane foam can be manufactured. * By using a specific amine catalyst and an organometallic catalyst in combination without using a silicone foam stabilizer and using an organotin catalyst at all, extremely high outgassing components and bleed-out even when exposed to a high temperature environment. Since a small amount of polyurethane foam is produced, it is particularly suitable for use as a soundproofing material and a packing material for a hard disk drive.

[Brief description of the drawings]

FIG. 1 is an explanatory view of an air leak test apparatus.

Continuation of the front page (72) Inventor Koichi Kusakawa 1170 Ako, Komagane-shi, Nagano F-term (reference) 4J034 CA02 CA17 CA32 CC29 CC34 DA01 DF02 DF11 DF16 DF20 DF22 DF29 DG02 DG03 DG04 DG05 DG14 GA05 GA06 HA07 HC03 HC12 HC17 HC22 HC52 HC64 HC67 HC71 HC73 KB02 KB05 KC02 KC35 KD02 KD11 NA05 QC01 RA15

Claims (7)

[Claims] 1. A polyurethane foam curable composition for obtaining a polyurethane foam by reacting a composition containing a polyol component and a polyfunctional isocyanate in the presence of a catalyst and a foaming agent. Is a reactive amine catalyst (A) having at least one hydroxy group or mercapto group in the molecule that reacts with a polyfunctional isocyanate and / or an amine catalyst having an acid dissociation constant pKa of 9 or more and having a strong gelation ( B) and potassium or sodium salt of octylic acid, naphthenic acid or octylate of iron (III), nickel or copper having a melting point or softening point of 150 ° C. or more, iron (III), nickel or acetylacetonate metal of copper At least one organometallic catalyst (C) selected from the group consisting of a salt and an alkoxytitanium ester compound having a Ti-OC bond. A curable composition of a polyurethane foam, wherein the curable composition has a low gas generating component and a low bleed-out component. 2. A reactive amine catalyst (A), which is a tertiary amine compound represented by the following general formula, and an acid dissociation constant pka having 2 to 10 carbon-carbon bonds in a bond between a nitrogen atom and a hydroxy group. Amine catalyst (B) with a strong gelation of 9 or more
The curable composition according to claim 1, wherein the curable composition is used in combination with the organometallic catalyst (C). Embedded image (Wherein, R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 10) 3. The curable composition for a polyurethane foam having a low gas generating component according to claim 1, wherein the highly gelling amine catalyst (B) is a tertiary amine compound having a boiling point of 180 ° C. or lower. 4. The polyurethane foam curable composition according to claim 1, wherein the highly gelling amine catalyst (B) is a triazine tertiary amine catalyst having a boiling point of 180 ° C. or lower. 5. The polyurethane foam according to claim 1, wherein the alkoxytitanium ester compound of the organometallic catalyst (C) is a compound having a butoxy group and an acetylacetonate group. Curable composition. 6. A reactive amine catalyst (A) having at least one hydroxy group or mercapto group in a molecule which reacts with a polyfunctional isocyanate, and / or an acid dissociation constant pKa of 9 or more. Strong amine catalyst (B)
Potassium or sodium salt of octylic acid, iron (III) having a melting point or softening point of 150 ° C. or higher, naphthenic acid or octylate of nickel, copper, iron (III), nickel, metal salt of acetylacetonate of copper, Ti-OC
A polyol component, a polyfunctional isocyanate, and a blowing agent in the presence of a catalyst comprising an organometallic catalyst (C) in a mixture selected from one or more of an alkoxy titanium ester compound having a bond. 2. The method for producing a polyurethane foam having a low gas generating component and a low bleed-out component according to claim 1, wherein the foam obtained by reacting the composition to be heated is subjected to a heat baking treatment. 7. A soundproofing material and a packing material for a hard disk drive, characterized by using a polyurethane foam having a low outgassing component and a low bleedout component according to each of the above claims.