JP6870529B2 - A catalyst composition for producing polyurethane foam, and a method for producing flexible polyurethane foam using the same. - Google Patents

Description

The present invention relates to a catalyst composition for producing polyurethane foam and a method for producing a flexible polyurethane foam using the same. More specifically, the present invention relates to a method for producing a flexible polyurethane foam having sufficient hardness, low compression strain property and low VOC (volatile organic compound) property in the production of flexible polyurethane foam.

Polyurethane foam is usually produced by reacting a polyol and an isocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a cross-linking agent and the like. Many metal compounds and tertiary amine compounds are used as catalysts in the production of polyurethane foams. These are widely used industrially when used alone or in combination.

In the production of polyurethane foams using water, a low boiling point organic compound or the like as a foaming agent, a tertiary amine compound is widely used as a catalyst because of its excellent productivity and moldability. Examples of such a tertiary amine compound include 1,4-diazabicyclo [2.2.2] octane (TEDA), N, N, N', N'-tetramethyl-1,6-hexanediamine, and the like. Examples thereof include bis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like (for example). , Non-Patent Document 1). On the other hand, as the metal-based compound, for example, an organometallic compound such as an organotin compound is often used. Productivity and moldability deteriorate, and some metal-based catalysts contain heavy metals such as lead, tin, and mercury, and there are concerns about toxicity problems and environmental problems due to heavy metals remaining in the product. In most cases, it is often used in combination with a tertiary amine catalyst, and metal-based catalysts are rarely used alone.

Polyurethane foam is required to have properties such as low odor, low VOC (volatile organic compound), low contamination with other materials, and high durability. Catalysts for the production of polyurethane foam have a significant effect on these properties.

The tertiary amine compound is gradually discharged from the polyurethane product as a volatile amine compound, which causes odor problems and discoloration problems of other materials (eg, skin PVC). In addition, the tertiary amine catalyst generally has a strong odor, and the working environment at the time of producing polyurethane foam and the environment at the site where the product is used are significantly deteriorated.

As a method for solving these problems, instead of the above-mentioned volatile tertiary amine catalyst, an amine catalyst having a hydroxy group, a primary amino group, or a secondary amino group that can react with isocyanate in the molecule (hereinafter referred to as an amine catalyst). , A method using a bifunctional cross-linking agent having a tertiary amino group in the molecule has been proposed (see, for example, Patent Documents 1 to 5). ..

In the method using a reactive catalyst, the reactive catalyst is immobilized in the skeleton of the polyurethane foam in the form of reacting with isocyanate, so that the odor of the final foam product is reduced and the discoloration of other materials (for example, epidermal PVC) is reduced. It is effective for.

By the way, permanent compressive strain can be mentioned as a durable physical property required for a soft and highly elastic foam used for an automobile cushion, which accounts for a large proportion of the use of the flexible polyurethane foam. When this permanent compression strain is inferior, the thickness of the cushion decreases over time, which causes problems such as changes in the position of the eyes of the vehicle driver and deterioration of sitting comfort and riding comfort. As an accelerated test method for this permanent compression strain, a moist heat aging resistance test (hereinafter, may be referred to as "wet set") is the mainstream.

Reactive catalysts tended to exacerbate permanent compressive strain as compared to conventional catalysts. In addition, since the activity is weak, the required amount is large, and there is a problem of cost increase.

As a conventional method for improving permanent compression strain, a method of increasing the number of functional groups of a polyoxyalkylene polyol or a method of increasing the degree of cross-linking of a flexible polyurethane foam by using a low molecular weight and polyfunctional cross-linking agent is known ( For example, see Patent Documents 6 to 8).

As a reactive catalyst with improved activity, the use of an amine compound having high resinification activity is known (for example, Patent Documents 9 to 10). As another highly active reactive catalyst, N, N-dimethyl-1,3-propanediamine is known (for example, Patent Document 11), but there is a problem that the hardness of the flexible polyurethane foam is lowered.

Japanese Unexamined Patent Publication No. 46-4846 Special Publication No. 61-31727 Japanese Patent No. 2971979 Japanese Unexamined Patent Publication No. 63-265909 Japanese Unexamined Patent Publication No. 2008-45113 Japanese Unexamined Patent Publication No. 2-115211 Special Fair 6-86514 Gazette JP-A-2007-332375 Japanese Unexamined Patent Publication No. 2010-0374888 Japanese Unexamined Patent Publication No. 2010-106192 Japanese Unexamined Patent Publication No. 2014-028946

Keiji Iwata "Polyurethane Resin Handbook" (First Edition, 1987) Nikkan Kogyo Shimbun, Ltd. p. 118

Although the low vinyl chloride discoloration property, catalytic activity, and durable physical characteristics have been improved in the production of the flexible polyurethane foam by the above method, further improvement has been desired. Further, regarding VOC, it has been desired to reduce not only the volatileness of amine compounds but also the volatileization of other organic compounds.

The present invention has been made in view of the above problems, and an object of the present invention is to improve low vinyl chloride discoloration property and durable physical characteristics with a small amount of catalyst, reduce volatilization of amine compounds and other organic compounds, and necessary. It is an object of the present invention to provide a method for producing a flexible polyurethane foam having hardness, and a catalyst composition used therein.

As a result of diligent research to solve the above problems, the present inventors have obtained vinyl chloride discoloration and durability with a small amount of catalyst when two specific amine compounds are used in combination as a catalyst composition for producing polyurethane foam. We have found that it is possible to obtain a flexible polyurethane foam product which is improved, reduces volatilization of amine compounds and other organic compounds, and has a required hardness, and has completed the present invention.

That is, the present invention relates to a catalyst composition for producing polyurethane foam as shown below, and a method for producing flexible polyurethane foam using the same.

[1] A catalyst composition for producing a polyurethane foam containing an amine compound represented by the following general formula (1), an amine compound represented by the following general formula (2), and polyethylene glycol.

[In the above general formula (1), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, hydroxymethyl groups, or 1 to 4 carbon atoms, respectively. Represents the alkoxy group of. m is 1 or 2. In the above general formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is an integer of 2-4. ]
[2] The catalyst composition according to the above [1], wherein ^{R 1} , R ² , R ³ and R ^{4 are hydrogen atoms.}

[3] The catalyst composition according to the above [1] or [2], wherein m is 1.

[4] The catalyst composition according to any one of the above [1] to [3], wherein ^{R 5} and R ^{6 are methyl groups.}

[5] The catalyst composition according to any one of the above [1] to [4], wherein n is 3.

[6] The ratio of the weight of the amine compound represented by the general formula (1) to the combined weight of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is 5. The catalyst composition according to any one of the above [1] to [5], which comprises ~ 65% by weight.

[7] The catalyst composition according to any one of the above [1] to [6], wherein the polyethylene glycol has a hydroxyl value of 160 to 1100.

[8] The amine compound represented by the general formula (1) and the general formula with respect to the total weight of the amine compound represented by the general formula (1), the amine compound represented by the general formula (2) and polyethylene glycol. The catalyst composition according to any one of the above [1] to [7], wherein the ratio of the total weight of the amine compound represented by (2) is 40 to 90% by weight.

[9] A method for producing a flexible polyurethane foam, which comprises reacting a polyol and an isocyanate in the presence of the catalyst composition and the foaming agent according to any one of the above [1] to [8].

[10] The amount of the catalyst composition used according to any one of the above [1] to [7] is in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyol. 9] The method for producing a flexible polyurethane foam.

[11] The method for producing a flexible polyurethane foam according to the above [9] or [10], wherein the isocyanate index is 60 to 130 and the foaming agent is water.

By using the catalyst composition of the present invention, a flexible polyurethane foam having improved vinyl chloride discoloration and durability, reduced volatilization of amine compounds and other organic compounds, low odor, and required hardness with a small amount of catalyst. Is obtained. Further, depending on the composition (formulation) of the polyol premix, a flexible polyurethane foam having improved hysteresis loss can be obtained. Therefore, the production method of the present invention is extremely effective in the production of flexible polyurethane foam, which requires suppression of contamination of vinyl chloride resin, reduction of VOC (volatile organic compounds), and improvement of compression strain.

Conventionally, although N, N-dimethyl-1,3-propanediamine has a problem of lowering the hardness of the flexible polyurethane foam, the flexible polyurethane foam produced by the catalyst composition of the present invention has a hardness. It is unexpected and surprising that it does not bring about a decline. Furthermore, it is surprising and surprising that the change of only the amine catalyst could reduce not only the volatilization of amine compounds but also the volatilization of other organic compounds.

Hereinafter, the present invention will be described in detail.

The catalyst composition for producing polyurethane foam of the present invention is characterized by containing the amine compound represented by the general formula (1), the amine compound represented by the general formula (2), and polyethylene glycol.

In the present invention, when the amine compound represented by the above general formula (1) contains an optically active substance, a diastereomer, and a geometric isomer, the mixture thereof and the isomer in which they are isolated are included. ..

In the above general formula (1), the substituents R ¹ , R ² , R ³ and R ⁴ may correspond to the above definitions and are not particularly limited, but for example, a hydrogen atom, a hydroxyl group, a hydroxymethyl group, and the like. Alkyl group having 1 to 4 carbon atoms (specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc.), carbon number Examples of 1 to 4 alkoxy groups (specifically, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, etc.) can be mentioned. Of these, from the viewpoint of catalytic activity in the production of polyurethane foam, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, and a methoxy group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is more preferable. is there.

In the present invention, the amine compound represented by the above general formula (1) is not particularly limited, but for example, the substituents R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms. compound represents a methyl group, an ethyl group or a hydroxymethyl group, compounds all are hydrogen atom of the substituents R ^1, R ^2, R ³ and R ⁴ can be mentioned as preferred. In the general formula (1), a compound where all substituents R ^1, R ^2, R ³ and R ⁴ is a hydrogen atom, on the catalyst activity in the polyurethane foam production is also preferred.

Specific examples of the amine compound represented by the general formula (1) include, for example, the following compounds, but the present invention is not limited thereto.

The method for producing the amine compound represented by the general formula (1) is not particularly limited, but it can be produced, for example, by a cyclization reaction of dihydroxyalkylpiperazines (for example, JP-A-2010-37325). reference).

Further, the amine compound represented by the above general formula (1) can be produced, for example, by the method described in Kimiya Geterotskicheskikh Soedinenil, 10, 1404 (1980), International Publication No. 95/18104, and the like. Further, intramolecular cyclization of ethylene oxide adducts of hydroxyalkylpiperazines induced by the methods described in Journal of Medicinal Chemistry (1993), 36 (15), 2075-2083 and JP-A-2010-1220887. It can also be manufactured by doing so.

The method for producing the amine compound represented by the above general formula (1) having a substituent can be produced by using the corresponding substituted piperazine. The method for producing the substituted piperazine can be produced by the above-mentioned known technique for synthesizing hydroxyalkyl piperazines and the like.

In the above general formula (2), the substituents R ⁵ and R ⁶ may correspond to the above definitions and are not particularly limited, but for example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an isopropyl. Examples include a group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a hydrogen atom, a methyl group, and an ethyl group are preferable.

In the above general formula (2), n is an integer of 2 to 4, preferably 2 to 3 and even more preferably 3 from the viewpoint of catalytic activity and availability.

In the present invention, the ratio of the weight of the amine compound represented by the general formula (1) to the combined weight of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is Although not particularly limited, it is usually preferably in the range of 5 to 65% by weight, more preferably 10 to 55% by weight, still more preferably 20 to 45% by weight, from the viewpoint of catalytic activity and volatileness of the catalyst. It is in the range of%. Here, the ratio of the weight of the amine compound represented by the general formula (1) to the combined weight of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is 5. When it is% by weight or more, the volatileness of the catalyst is low, which is preferable, and when it is 65% by weight or less, the catalytic activity is high, which is preferable.

The hydroxyl value of the polyethylene glycol used in the catalyst composition of the present invention is not particularly limited, but is usually preferably in the range of 160 to 1110, and the solubility of the amine compound represented by the above general formula (1). From the viewpoint of ease of handling of the catalyst composition due to compatibility and viscosity, it is more preferably 260 or more, more preferably 350 or more, and further preferably 400 or more. Further, from the viewpoint of the effect of improving the durability physical characteristics, it is preferably 800 or less, more preferably 600 or less.

The amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) with respect to the total weight of the amine compound represented by the general formula (1), the amine compound represented by the general formula (2) and polyethylene glycol. The ratio of the total weight of the amine compound represented by (1) is not particularly limited, but is usually preferably in the range of 40 to 90% by weight, more preferably 50, from the viewpoint of storage stability and catalytic activity. It is in the range of ~ 80% by weight, more preferably 55 to 70% by weight. Here, when the content of the amine compound represented by the general formula (1) and the general formula (2) is 90% by weight or less, the amine compound represented by the general formula (1) in the catalyst composition is present. It is less likely to precipitate during long-term storage or storage at a low temperature, and has excellent storage stability. When it is 40% by weight or more, the catalytic activity is high, which is preferable.

The catalyst composition of the present invention contains a solvent in addition to the amine compound represented by the general formula (1), the amine compound represented by the general formula (2), and polyethylene glycol without departing from the spirit of the present invention. Can be made to. Examples of such a solvent include, but are not limited to, low molecular weight polyhydric alcohols other than polyethylene glycol and water, and examples thereof include ethylene glycol, propylene glycol, polypropylene glycol, and 1,4-butanediol. And glycerin.

As the catalyst composition of the present invention, other catalysts other than the amine compound represented by the general formula (1), the amine compound represented by the general formula (2) and polyethylene glycol, as long as the gist of the present invention is not deviated. (Ingredient) can be contained. Examples of such a catalyst include conventionally known organometallic catalysts, tertiary amine catalysts, and the like.

Examples of such an organic metal catalyst include stanus diacetate, stanus dioctate, stanus diolaate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, and the like. Examples thereof include lead octanate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

The tertiary amine catalyst may be any conventionally known one, and is not particularly limited. For example, triethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N-tetramethylpropylenediamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N ", N" -pentamethyldipropylene triamine, N, N, N', N'-tetramethylguanidine, 1 , 3,5-Tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, N, N'-dimethylpiperazin, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1, 2-Dimethylimidazole, 1-isobutyl-2-methylimidazole, N, N, N'-trimethyl-N'-(2-hydroxyethyl) bis (2-aminoethyl) ether, N- (3-aminopropyl)- Examples thereof include tertiary amine compounds such as N, N', N'-trimethyl-2,2'-oxybis (ethylamine). Of these, in terms of catalytic activity, triethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N'-trimethyl-N'-(2-hydroxyethyl) bis (2-aminoethyl) ether, N, N, N', N'-tetramethylhexamethylenediamine are particularly preferred.

The catalyst composition of the present invention is used to promote a urethanization reaction (resination reaction) between polyols and isocyanates, a urea conversion reaction (foaming reaction) between isocyanates and water, and the like.

Next, a method for producing a flexible polyurethane foam using the above-mentioned catalyst composition of the present invention will be described.

The method for producing a flexible polyurethane foam of the present invention is characterized in that a polyol and an isocyanate are reacted in the presence of the above-mentioned catalyst composition of the present invention and a foaming agent.

In the present invention, the flexible polyurethane foam generally refers to a reversibly deformable foam having an open cell structure and exhibiting high air permeability [Gunter Oertel, "Polyurethane Handbook" (1985 edition) Hanser Publishing (Germany)). , P. 161 to 233 and Keiji Iwata "Polyurethane Resin Handbook" (first edition in 1987) Nikkan Kogyo Shimbun, p. See description 150-221]. The physical properties of the flexible urethane foam are not particularly limited, but generally, the density is in the range of 10 to 100 kg / m ³ , the compressive strength (ILD 25%) is 200 to 8000 kPa, and the elongation rate is 80 to 500%. Is.

In the production method of the present invention, the amount of the catalyst composition of the present invention used is not particularly limited, but when the polyol used is 100 parts by weight, it is usually 0.01 to 30 parts by weight, preferably 0.01 to 30 parts by weight. Is in the range of 0.05 to 15 parts by weight. If a large amount of the catalyst composition of the present invention is used, the productivity of the polyurethane foam is improved, but the reactivity may become too fast and the mold may not be closed in time. If the amount of the catalyst composition of the present invention used is small, the productivity of the polyurethane foam is inferior.

Examples of the polyol used in the production method of the present invention include polyether polyols, polyester polyols, polymer polyols and the like. Furthermore, flame-retardant polyols such as phosphorus-containing polyols and halogen-containing polyols can be used in combination.

Polyether polyols are obtained, for example, by subjecting glycerin, trimethylolpropane and the like to an addition reaction of alkylene oxides such as ethylene oxide and propylene oxide. p. It can be produced by the method described in 42-53.

As polyester polyols, those obtained by dehydration condensation reaction between dibasic acid (mainly adipic acid), glycol and triol, and Keiji Iwata "Polyurethane Resin Handbook" (first edition in 1987), Nikkan Kogyo Shimbun, p. Examples thereof include the waste products produced in nylon described in 117, trimethylolpropane, pentaerythritol waste products, phthalic acid-based polyester waste products, polyester polyols derived by treating waste products, and the like.

Examples of the polymer polyol include a polymer polyol obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, and styrene in the presence of a radical polymerization catalyst.

Examples of the flame-retardant polyol include a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, epichlorohydrin, a halogen-containing polyol obtained by ring-opening polymerization of trichlorobutylene oxide, and a phenol polyol.

Of these, a combination of a polyether polyol and a polymer polyol is particularly preferable. Further, the average molecular weight of the polyether polyol is more preferably 3000 to 15000.

Examples of the isocyanate used in the production method of the present invention include aromatic diisocyanates such as toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), isomers thereof, polynuclear compounds and mixtures thereof.

Examples of TDI and its derivative include a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, a terminal isocyanate prepolymer derivative of TDI, and the like. Examples of MDI and its derivative include a mixture of MDI and its polymer polyphenyl-polymethylene diisocyanate, a diphenylmethane diisocyanate derivative having a terminal isocyanate group, and the like. Of these, it is particularly preferable to use TDI or a derivative thereof in combination with MDI or a derivative thereof, or to use MDI or a derivative thereof alone because productivity is improved.

The ratio of isocyanate to polyol used is not particularly limited, but is preferably in the range of 60 to 130 in terms of isocyanate index (isocyanate group / active hydrogen group capable of reacting with isocyanate group).

The foaming agent used in the production method of the present invention is not particularly limited, but for example, 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1,3,3-penta. Fluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2, 3,3,3-Heptafluoropropane (HFC-227ea), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3 3,3-Pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3 3,3-Hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yz), Freon compounds such as 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), HFE Examples thereof include hydrofluoroethers such as -254 pc, low boiling hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, acetone and the like. These may be used alone or in combination of two or more. As the low boiling point hydrocarbon, a hydrocarbon having a boiling point of -30 to 70 ° C. is usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane and mixtures thereof. Of these, water is preferred in the present invention.

The amount of the foaming agent used is determined according to the desired density and the physical characteristics of the foam, and is not particularly limited, but in general, the obtained foam density is usually 5 to 1000 kg / m ³ , preferably. It is selected to be in the range of 10 to 500 kg / m ^3.

If necessary in the production method of the present invention, a surfactant can be used. Examples of the surfactant include conventionally known organic silicone-based surfactants, and the amount used thereof is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyol.

In the production method of the present invention, a cross-linking agent or a chain extender can be added if necessary. The cross-linking agent or chain extender may be a low molecular weight polyhydric alcohol (eg, 1,4-butanediol, glycerin, etc.), a low molecular weight amine polyol (eg, diethanolamine, triethanolamine, etc.), or a polyamine (eg, eg, diethanolamine, triethanolamine, etc.). Ethylenediamine, xylylenediamine, methylenebis orthochloroaniline, etc.) can be mentioned. Of these, diethanolamine and triethanolamine are preferable.

In the production method of the present invention, as described above, the catalyst composition of the present invention can be used alone or mixed with the above-mentioned solvent and other catalysts (components). In the production method of the present invention, the catalyst composition thus prepared may be added to the polyols and used, or individual components may be separately added to the polyols and used, particularly. There is no limit.

In the production method of the present invention, a colorant, a flame retardant, an antiaging agent, a communicating agent, other known additives and the like can also be used, if necessary. As long as the types and amounts of these additives do not deviate from the known formats and procedures, they can be sufficiently used within the range normally used.

In the production method of the present invention, usually, a mixed solution prepared by mixing the catalyst composition of the present invention and the above-mentioned raw materials such as polyol, isocyanate and foaming agent is rapidly mixed and stirred, and then injected into an appropriate container or mold. It is performed by foam molding. Mixing and stirring may be carried out using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, for example, a high-pressure, low-pressure, or spray-type device is used.

The products produced by the production method of the present invention can be used for various purposes. Specific applications include crash pads, mattresses, seats, automobile-related seats, headrests and the like.

The present invention will be described in more detail based on the following examples, but the present invention is not construed as being limited thereto. In addition, (pbw) in the table shows the part by weight of the other agent when the polyol is 100 parts by weight.

1,4-diazabicyclo [2.2.2] octane-2-methanol (hereinafter referred to as “exemplified compound 1”) was synthesized by a conventionally known method.

Examples 1 to 4, Reference Examples 1 to 2.
Two types of premixes were prepared according to the raw material mixing ratios shown in Tables 1 and 2.

Table 4 shows an example of producing a flexible polyurethane foam using the catalyst components shown in Table 3.

The premix was placed in a 300 mL polyethylene cup, the catalyst composition was further added, and the temperature was adjusted to 20 ° C. The amount of the catalyst composition is such that the reactivity is 59 ± 2 seconds in the following gel time, and in Formulation 1, the catalyst 3 is added so as to match the rise profile. The isocyanate solution whose temperature was adjusted to 20 ° C. in a separate container was placed in a premix cup, and the mixture was quickly stirred with a stirrer at 6000 rpm for 5 seconds. The mixed solution mixed and stirred was transferred to a 2 L polyethylene cup whose temperature was adjusted to 60 ° C., and the reactivity during foaming was measured by the method shown below.

The measurement method and evaluation method in Examples and Reference Examples are as follows.

[Measurement of reactivity]
・ Cream time:
The foaming start time and the foam start time were visually measured.

・ Gel time:
The time required for the reaction to proceed and change from a liquid substance to a resinous substance was measured.

・ Rise time:
The time at which the foam stopped rising was measured using a laser displacement sensor (manufactured by KEYENCE, model: LF-2510).

^{Next, the total foam density was 45 ± 2 kg / m 3} in Formulation 1 in a mold (inner dimensions, made of aluminum with internal dimensions of 25 x 25 x 8 cm) whose temperature was adjusted to 60 ° C by increasing the raw material scale. In Formulation 2, the mixed solution was added so as to be 51 ± 2 kg / m ³ , the lid was closed, and foam molding was performed. The foam was demolded 7 minutes after the mixture was added. The physical characteristics of the molded foam were measured by the methods shown below.

[Physical characteristics of form]
・ Overall density:
The molded foam was weighed and divided by volume.

・ ILD:
It was carried out according to ISO2439B. After crushing the molded foam (3 times at 75%), the load required to compress to 25% or 65% was measured.

・ Ball rebound (rebound elasticity):
A steel ball with a diameter of 16 mm and a mass of 16 g is dropped from a height of 470 mm onto a molded foam, and the maximum height at which it bounces is recorded. The impact resilience was calculated by the following formula.

Ball rebound (%) = D / C x 100
C: Height at which the steel ball is dropped (mm)
D: Maximum height (mm) that bounced off.

・ Core density:
Cut 20 x 20 x 5 cm from the center of the molded foam to make the core part. The core was weighed and divided by volume.

・ CLD:
It was carried out according to ISO3386 / 1. After crushing the core portion (3 times at 75%), the load required to compress the core portion to 40% was measured.

-Tensile strength of foam A predetermined foam with a size of 1 x 1 x 10 cm is cut from the foam whose foam core density is measured to make a test piece, and a tensile test is performed according to JIS K7311-1995 to determine the tensile strength. It was measured.

-Stretching of foam A predetermined foam having a size of 1 x 1 x 10 cm was cut from the foam for which the foam core density was measured to obtain a test piece, and a tensile test was carried out according to JIS K7311-1995 to measure the elongation.

-Tear strength of foam A predetermined foam with a size of 1 x 1 x 10 cm is cut from the foam whose foam core density is measured to make a test piece, and a tear test is performed according to JIS K7311-1995 to determine the tear strength. It was measured.
-Hysteresis loss: Hysteresis loss is measured using a foam and a testing machine whose foam hardness has been measured. As precompression, 100 mm / min. The disk is moved up and down at the speed of, and a compression operation corresponding to 65% of the foam thickness is performed once. Hysteresis loss measurement is performed by the second compression operation to obtain the stress-strain curve during pressurization and the stress-strain curve during decompression, and the stress-strain curves during pressurization and decompression obtained by this operation are individually obtained. Hysteresis loss [= (integrated value of stress-strain curve during pressurization-integrated value of stress-strain curve during decompression) / integrated value of stress-strain curve during pressurization x 100] was obtained. .. A foam with low hysteresis loss was judged to have high elasticity.

[Durability of foam]
Wet-CS was measured as the durability (weather resistance) of the foam. This is to measure how much permanent compression strain remains when the polyurethane resin is compressed under moist heat deterioration conditions for a certain period of time. Therefore, it can be said that the smaller this value is, the better the durability is.

From the above core part, a foam is cut to a size of 5 cm in length, 5 cm in width, and 2.5 cm in thickness, and this is subjected to a compression test of 50% in the thickness direction for 22 hours under the conditions of 50 ° C. and 95% relative humidity. And the dimensional change rate was measured. Wet-CS is calculated by the following formula.

Wet-CS (%) = (AB) / A × 100.
A: Initial thickness (cm)
B: Thickness (cm) after the compression test.

[PVC pollution]
The PVC contamination test was based on VW PVC3937. First, a 7 × 7 × 3 cm foam is cut out from the upper part of the foam obtained by mold foaming (3 days after production), placed in a 2 liter separable flask, and a 3 × 3 cm vinyl chloride sheet is hung from the upper lid, and then the flask. Was sealed. This flask was heated at 100 ° C. for 72 hours, allowed to cool, and then the discoloration of the vinyl chloride sheet was measured using a color difference meter (ZE2000 manufactured by Nippon Denshoku Co., Ltd.).

[Odor]
The foam cut into 6 × 6 × 12 cm was placed in a 5 L nitrogen-filled 10 L Tedlar bag, and after heating at 65 ° C. × 72 hours, the odor in the Tedlar bag was smelled by 10 people. The intensity and quality of the odor were based on the following criteria, and the average value of the results of each person was calculated.

Intensity of odor: 5 Strong odor >> 3 Easily perceptible odor >> 0 Odorless Odor quality: 4 Extremely pleasant >> 0 Neither pleasant nor unpleasant >> -4 Extremely unpleasant [volatile amount of organic compounds]
Based on VDA278, it was analyzed by the Tokai Technical Center. A 15 mg foam sample was placed in a heat desorption device, and the organic compounds released by heating were observed by GC-MS. VOC is the amount of organic compounds volatilized and observed at 90 ° C. × 30 minutes and FOG at 120 ° C. × 60 minutes following VOC measurement, VOC is calculated as a toluene equivalent value, and FOG is calculated as a hexadecane equivalent value.

As is clear from the comparison between Examples 1 to 4 and Reference Examples 1 and 2 in Table 4, the present invention contains the example compound 1, polyethylene glycol, and N, N-dimethyl-1,3-propanediamine. In the examples using the catalyst composition, the required amount of catalyst was reduced (that is, high catalytic activity) as compared with Reference Examples 1 and 2 containing no N, N-dimethyl-1,3-propanediamine in the same formulation. showed that). The higher the ratio of N, N-dimethyl-1,3-propanediamine, the smaller the required amount of catalyst.

Further, regarding hardness, ball rebound, tensile strength, tensile elongation, tear strength and hysteresis loss, the examples were equivalent or improved in the same formulation as those of the reference examples.

For Wet-CS, the examples were equivalent or improved in the same formulation as compared to the reference examples. The higher the ratio of N, N-dimethyl-1,3-propanediamine, the better the Wet-CS.

Furthermore, regarding PVC contamination, the examples were improved as compared with the reference examples.

The intensity of odor was small in both Examples and Reference Examples, and the quality of odor was close to a value (0) that was neither pleasant nor unpleasant in either Example or Reference Example.

Moreover, regarding the volatilization of the organic compound, the examples were greatly improved as compared with the reference examples.

The flexible polyurethane foam produced by using the catalyst composition of the present invention is useful for producing car seats used as automobile interior materials and the like.

Claims (11)

A catalyst composition for producing a polyurethane foam containing an amine compound represented by the following general formula (1), an amine compound represented by the following general formula (2), and polyethylene glycol.

[In the above general formula (1), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, hydroxymethyl groups, or 1 to 4 carbon atoms, respectively. Represents the alkoxy group of. m is 1 or 2. In the above general formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is an integer of 2-4. ] The catalyst composition according to claim ¹ , wherein R ^{1, R 2} , R ³ and R ^{4 are hydrogen atoms.} The catalyst composition according to claim 1 or 2, wherein m is 1. The catalyst composition according to any one of claims 1 to 3, wherein R ⁵ and R ^{6 are methyl groups.} The catalyst composition according to any one of claims 1 to 4, wherein n is 3. The ratio of the weight of the amine compound represented by the general formula (1) to the combined weight of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is 5 to 65 weight. The catalyst composition according to any one of claims 1 to 5, wherein the content is%. The catalyst composition according to any one of claims 1 to 6, wherein the polyethylene glycol has a hydroxyl value of 160 to 1100. The amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) with respect to the total weight of the amine compound represented by the general formula (1), the amine compound represented by the general formula (2) and polyethylene glycol. The catalyst composition according to any one of claims 1 to 7, wherein the ratio of the combined weight of the amine compound represented by (1) to 40 to 90% by weight is 40 to 90% by weight. A method for producing a flexible polyurethane foam, which comprises reacting a polyol and an isocyanate in the presence of the catalyst composition and the foaming agent according to any one of claims 1 to 8. The ninth aspect of the present invention, wherein the amount of the catalyst composition used according to any one of claims 1 to 7 is in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyol. A method for manufacturing a flexible polyurethane foam. The method for producing a flexible polyurethane foam according to claim 9 or 10, wherein the isocyanate index is 60 to 130 and the foaming agent is water.