JP4104501B2 - Production method of polyurethane foam - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyurethane foam. More specifically, seat cushions, headrests, armrests, floor mats, instrument panels, dash silencers, automotive interior materials such as handle skins, bedding, furniture cushions, building materials, freezer warehouses, bathtub insulation, etc. The present invention relates to a process for producing a polyurethane foam which can be suitably used.
[0002]
[Prior art]
Soft and semi-rigid polyurethane foams are used as automobile interior materials because they have moderate impact absorption, elasticity, compression recovery rate, sound absorption, and the like. In recent years, the reduction of volatile organic compounds (hereinafter referred to as VOC) represented by formaldehyde and toluene has been studied in consideration of the effects on the human body in enclosed spaces such as automobiles and houses. ing.
[0003]
Soft and semi-rigid polyurethane foams used as interior materials for automobiles are also subject to this VOC reduction. VOCs are mainly attributed to the use of amine-based catalysts during the production of polyurethane foams. There is a demand for a reduction in this.
[0004]
In general, the fogging phenomenon that occurs in automobile window glass called fogging that occurs when the temperature inside the automobile rises is due to amine-based catalysts such as triethylenediamine and bis (2-dimethylaminoethyl) ether. VOC is thought to be the cause. As a method for eliminating this fogging, a method has been proposed in which an amine-based catalyst itself is incorporated into the structure of a polyurethane foam using an amine-based catalyst having a functional group such as a hydroxyl group or amino group that reacts with isocyanate in the molecule ( For example, see Patent Document 1).
[0005]
Furthermore, there is a need for a polyurethane foam that reduces both the amount of VOCs generated from amine-based catalysts from polyurethane foam used in automobile interior materials and the like, and achieves both moldability and curability.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 2000-319435
[Problems to be solved by the invention]
The present invention reduces the amount of VOC based on amine-based catalyst from polyurethane foam even at high temperature, makes fogging difficult, has good heat resistance, and has a wide and thin shape. Even so, an object is to provide a method capable of producing a polyurethane foam excellent in curability and moldability.
[0008]
[Means for Solving the Problems]
The present invention relates to formula (I):
(CH ₃ ) ₂ N (CH ₂ ) _p OH (I)
(Wherein p represents an integer of 4 to 9)
And a compound represented by formula (II):
^{HO- [R 1 -N (R 2} )] n -R 1 -OH (II)
[In the formula, R ¹ is the same or different C 2-24 linear or branched alkylene group, alicyclic alkylene group, cycloalkylene group, aralkylene group or formula:
[0009]
[Chemical formula 2]
[0010]
(Wherein, R ³ is a hydrogen atom or a methyl group, R ⁴ are identical or different straight-chain or branched-chain alkylene group having a carbon number of 2 to 24, alicyclic alkylene group, cycloalkylene group or aralkylene group, x is an average Degree of polymerization, indicating a number from 0 to 15)
R ² is the same or different C 1-9 linear or branched alkyl group or aralkyl group, n is the average degree of polymerization, and represents a number of 2-50.
And a process for producing a polyurethane foam in which a polyol component and an isocyanate component are reacted in the presence of a catalyst containing a compound represented by the formula:
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is characterized in that a catalyst containing a compound represented by the formula (I) and a compound represented by the formula (II) is used as the catalyst.
[0012]
The compound represented by formula (I) and the compound represented by formula (II) are both amine-based catalysts having a hydroxyl group in the molecule. In the compound represented by the formula (I), a group having 4 or more carbon atoms is further interposed between the nitrogen atom of the amino group and the hydroxyl group. The compound represented by the formula (II) has two or more tertiary amino groups and two hydroxyl groups.
[0013]
In the present invention, since the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the amount of VOC generated based on the amine-based catalyst can be almost eliminated, and fogging can be prevented. In addition to making it difficult to generate, there is an exceptionally excellent effect that a polyurethane foam excellent in curability and moldability can be obtained even if the heat resistance is good and the shape is wide and thin. .
[0014]
The reason why such an excellent effect is exhibited is not clear, but the compound represented by the formula (I) has a group having 4 or more carbon atoms between the nitrogen atom of the amino group and the hydroxyl group. Therefore, the reactivity of the hydroxyl group in the catalyst molecule is not easily affected by the nitrogen atom, so it reacts efficiently with the isocyanate component, and is almost taken into the polyurethane foam by chemical bonding. The urethane bond formed by the reaction of the hydroxyl group with the isocyanate component is also separated by the presence of a group having 4 or more carbon atoms from the nitrogen atom of the amino group, and is represented by the formula (II) Since the compound has a high vapor pressure and two hydroxyl groups, since at least one hydroxyl group reacts with the isocyanate component, it is incorporated into the polyurethane foam by a chemical bond. The compound represented by the formula (II) and the compound represented by the formula (II) hardly scatter, so the generation amount of VOC based on the amine-based catalyst can be almost eliminated, fogging hardly occurs, and thermal deterioration of the polyurethane Is also considered to be suppressed.
[0015]
Further, usually, when the catalyst molecule has an active group that reacts with an isocyanate component such as a hydroxyl group, the catalyst is incorporated into the polyurethane foam by a chemical bond with the progress of the reaction, so that the catalytic activity is lowered.
[0016]
However, when the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the characteristics of both are derived synergistically, and in the initial stage of the reaction, the resinification reaction is preferentially cured. It is considered that the reactivity reduction of the resinification reaction and the foaming reaction can be suppressed more than expected even when the reaction is late. These effects increase in the area where the reactivity of the foaming reaction is relatively lower than the reactivity of the resinification reaction, for example, in the vicinity of the foam skin where the temperature is relatively low during polyurethane foam production. It is considered that a remarkable effect is exhibited in the case of a foam shape having a large volume in the vicinity.
[0017]
Therefore, the time-dependent balance between the resinification reaction and the foaming reaction, which is a competitive reaction, is good, and since the reaction behavior in the vicinity of the skin of the foam is excellent, even in a wide and thin shape, It is considered that both curability and moldability can be achieved.
[0018]
In the compound represented by the formula (I), p represents an integer of 4 to 9.
Specific examples of the compound represented by the formula (I) include 4-dimethylamino-1-butanol, 6-dimethylamino-1-hexanol, 8-dimethylamino-1-octanol, 9-dimethylamino-1-nonanol. These compounds can be used alone or in admixture of two or more. Among these, 6-dimethylamino-1-hexanol is preferable from the viewpoint of catalytic activity and low odor.
[0019]
In the compound represented by the formula (II), R ¹ is the same or different linear or branched alkylene group having 2 to 24 carbon atoms, alicyclic alkylene group, cycloalkylene group, aralkylene group, or the formula:
[0020]
[Chemical 3]
[0021]
Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is the same or different C 2-24 linear or branched alkylene group, alicyclic alkylene group, cycloalkylene group or aralkylene group, x is an average Degree of polymerization, a number from 0 to 15, preferably a number from 0 to 10)
The group represented by these is shown.
[0022]
Among R ¹ , a linear or branched alkylene group having 2 to 9 carbon atoms is preferable, and a linear or branched alkylene group having 6 to 9 carbon atoms is more preferable from the viewpoint of catalytic activity and moldability.
[0023]
R ² represents the same or different straight-chain or branched-chain alkyl group or aralkyl group having 2 to 9 carbon atoms having 1 to 9 carbon atoms. Among R ² , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable from the viewpoint of expression of catalyst performance.
[0024]
n is an average degree of polymerization and shows the number of 2-50. n is preferably a number of 2 to 10, more preferably a number of 2 to 7, from the viewpoint of catalyst performance and handling viscosity.
[0025]
From the above viewpoints, in formula (II), R ¹ is a linear or branched alkylene group having 2 to 9 carbon atoms, and R ² is a linear or branched alkyl group having 1 to 4 carbon atoms. , N is preferably a number of 2 to 10, R ¹ is a linear or branched alkylene group having 6 to 9 carbon atoms, R ² is a methyl group, and n is a number of 2 to 7. More preferably.
[0026]
The compound represented by the formula (II) can be obtained by dehydrating and condensing a diol, which is a raw material for production, and a primary amine under a catalyst having a copper-noble metal as a main component. In addition, the compound which has various structures and molecular weight can be obtained by changing the kind and molar ratio of diol and primary amine. More specifically, for example, in the presence of a catalyst having a copper-nickel-platinum composition, a predetermined amount of methylamine and an appropriate amount of hydrogen gas are continuously blown into 1,6-hexanediol to produce a condensation reaction. The compound represented by the formula (II) can be obtained by reacting with stirring at a temperature of 150 to 200 ° C. under atmospheric pressure while continuously removing water from the reaction system.
[0027]
The weight ratio of the compound represented by the formula (I) and the compound represented by the formula (II) [compound represented by the formula (I) / compound represented by the formula (II)] is a molding of polyurethane foam. From the viewpoint of the property and curability, it is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 80/20.
[0028]
The total weight of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably based on 100 parts by weight of the polyol component from the viewpoint of enhancing the reactivity and maintaining the strength of the polyurethane foam. Is 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, still more preferably 0.3 to 5 parts by weight.
[0029]
The catalyst contains a compound represented by the formula (I) and a compound represented by the formula (II), and comprises a compound represented by the formula (I) and a compound represented by the formula (II). It is preferable to be configured.
[0030]
As long as the object of the present invention is not hindered, other catalysts may be contained, and the content varies depending on the type and the type and density of the target polyurethane foam. Therefore, it is desirable to appropriately adjust depending on the type of these other catalysts.
[0031]
Examples of other catalysts include organometallic compounds represented by organotin catalysts such as tin dibutyldiacetate, tin dioctanoate and tin dibutyldilaurate; 1,4-diazabicyclo [2.2.2] octane, 2-methyl- 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, N-ethylmorpholine, N- (dimethylaminoethyl) morpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N-dimethylpiperazine, N, N ', N'-trimethylaminoethylpiperazine, tris (3- Dimethylaminopropyl) amine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N, N ', N'',N''-pentamethylcyethylenetriamine, bis (2-dimethylaminoethyl ) Ether, 1,8-diazabicyclo [5.4.0] undecene-7, N, N ', N''-tris (3-dimethylaminopropyl) hexahydro-s-triazine, 5-dimethylamino-3-methyl-1-pentanol, N, N-dimethylethanolamine, 2- [2- (Dimethylamino) ethoxy] ethanol, 2- [2- (2- (dimethylamino) ethoxy) ethoxy] ethanol, N- (3-dimethylaminopropyl) -N-methylaminoethanol, N- (2-dimethylaminoethyl ) -N-methylaminoethanol, 1-methylimidazole, 1-isobutyl-2-methylimidazole, tertiary amine catalysts such as 1,2-dimethylimidazole and their derivatives, and salts thereof with carboxylic acid, carbonic acid, etc. Etc.
[0032]
As a polyol component, when manufacturing a polyurethane foam, what is conventionally used can be illustrated.
[0033]
Representative examples of the polyol component include polyester polyols, polyether polyols, polymer polyols, and phenol resin polyols described in “Polyurethane Resin Handbook” edited by Keiji Iwata (September 25, 1987, Nikkan Kogyo Shimbun). , Mannich polyol and the like, and these can be used alone or in admixture of two or more.
[0034]
Among the polyol components, polyether polyols, polymer polyols, polyester polyols, and the like are preferable, and polyether polyols and polymer polyols are more preferable, from the viewpoint of imparting a soft feel and design with a texture.
[0035]
Typical examples of the polyether polyol include polyoxypropylene-based polyol (hereinafter referred to as PPG), polyoxytetramethylene glycol (hereinafter referred to as PTMG), and mixtures thereof. Of these, PPG having ethylene oxide added to the terminal is preferable. The PPG polyoxypropylene / polyoxyethylene ratio (weight ratio) is preferably 50/50 to 95/5, more preferably 60/40 to 80/20, from the viewpoints of hydrolyzability, reactivity and foam strength. It is.
[0036]
Typical examples of the polymer polyol include those in which polymer fine particles obtained by polymerizing a polymerizable unsaturated group-containing monomer are dispersed in a polyether polyol. This is, for example, a method of mixing and dispersing polymer fine particles obtained by polymerizing a polymerizable unsaturated group-containing monomer and a polyether polyol, and polymerizing the polymerizable unsaturated group-containing monomer in the polyether polymer. By making it, it can manufacture by the method etc. which disperse | distribute the polymer fine particle obtained from the polymerizable unsaturated group containing monomer in polyether polyol. Among these methods, the latter method is preferable because a polymer polyol in which polymer fine particles are uniformly dispersed in the polyether polyol can be easily obtained. As the polymer fine particles, polystyrene, polyacrylonitrile and styrene-acrylonitrile copolymer are preferable.
[0037]
Examples of the polymerizable unsaturated group-containing monomer include alkyl (meth) acrylates having 1 to 4 carbon atoms in the alkyl group such as styrene; acrylotolyl; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. These monomers can be used alone or in admixture of two or more.
[0038]
The average hydroxyl value of the polyol component is preferably 14 to 100 mgKOH / g, more preferably 17 to 75 mgKOH / g, and still more preferably 17 to 70 mgKOH / g, from the viewpoint of imparting viscosity and elasticity to the foam.
[0039]
If necessary, additives such as a foam stabilizer, a communication agent, a crosslinking agent, a flame retardant, a stabilizer, a pigment, a filler, a viscosity reducer, a compatibilizing agent, and the like are appropriately added to the polyol component in an appropriate amount. May be.
[0040]
Although a foam stabilizer can be used as needed, what is necessary is just what is generally used when manufacturing a polyurethane foam.
[0041]
Representative examples of foam stabilizers include silicone surfactants such as dimethylpolysiloxane and polyoxyalkylene-modified dimethylpolysiloxane, anionic surfactants such as fatty acid salts, sulfate ester salts, phosphate ester salts, and sulfonates. These may be used alone or in admixture of two or more.
[0042]
Since the amount of the foam stabilizer varies depending on the type and the type and density of the target polyurethane foam and cannot be determined unconditionally, it is desirable to appropriately adjust according to the type of the foam stabilizer. .
[0043]
As the stabilizer, those generally used when producing polyurethane foam can be used as necessary. From the viewpoint of improving foam strength, triphenyl phosphite and pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] can be suitably used, and it is particularly preferable to use these in combination.
[0044]
Since the amount of the stabilizer used varies depending on the type and the type and density of the target polyurethane foam and cannot be determined unconditionally, it is desirable to adjust appropriately according to the type of the stabilizer.
[0045]
Examples of the isocyanate component include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, and naphthylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; hydrogenated diphenylmethane Aliphatic polyisocyanates such as diisocyanates, hydrogenated tolylene diisocyanates, isophorone diisocyanates; the above polys containing one or more of urethane bonds, carbodiimide bonds, uretoimine bonds, allophanate bonds, urea bonds, burette bonds, isocyanurate bonds, etc. Isocyanate modified products, etc., these should be used alone or in admixture of two or more It can be.
[0046]
In addition, when manufacturing automotive instrument panels and handle skins, among the isocyanate components, tolylene diisocyanate, diphenylmethane diisocyanate and their urethane bonds, carbodiimides, from the viewpoint of imparting moderate elasticity and textured design. A polyisocyanate-modified product containing one or more of bonds and the like is preferable.
[0047]
The amount of the isocyanate component varies depending on the required properties of the polyurethane foam and cannot be determined in general, but is usually adjusted so that the ratio (isocyanate index) of the polyol mixture and the isocyanate component described later is 30 to 110. Is preferable, 80 to 105 is more preferable, and 95 to 105 is more preferable.
[0048]
Water can be suitably used as the foaming agent. Other than water, as long as the object of the present invention is not hindered, low-boiling hydrocarbons such as isopentane, normal pentane and cyclopentane, gases such as nitrogen gas, air and carbon dioxide, HCFC-141b and HFC-134a , HFC-245fa, HFC-245ca, HFC-236ea, HFC-365mfc, HFE-347 and the like may be used.
[0049]
Since the amount of the foaming agent varies depending on the foam density of the target polyurethane foam and cannot be determined unconditionally, it is preferably adjusted as appropriate according to the target foam density.
[0050]
A polyurethane foam can be produced by reacting a polyol component and an isocyanate component in the presence of a catalyst containing a compound represented by the formula (I) and a compound represented by the formula (II) and a blowing agent. . For example, the polyurethane foam is a mixture of a polyol component, a catalyst, a foaming agent, and an additive as necessary, and the resulting polyol mixture and an isocyanate component are mixed and stirred with a molding machine or the like, and injected into a mold. It can be manufactured by foaming. More specifically, the polyol mixture is mixed and stirred using a tank or the like, and is usually adjusted to a temperature of about 20 ° C., and then the isocyanate is obtained using a foaming machine such as an automatic mixing injection foaming machine or an automatic mixing type injection foaming machine. Examples include a method of reacting with components and foaming.
[0051]
The polyurethane foam of the present invention thus obtained reduces the amount of VOC generated based on the amine-based catalyst even at high temperatures, is less prone to fogging, has good heat resistance, and has a wide and thin shape. However, it is excellent in curability and moldability. Therefore, the polyurethane foam of the present invention can be suitably used as an automobile interior material, various cushion materials, various heat insulating materials and the like.
[0052]
【Example】
Examples 1-3 and Comparative Examples 1-5
80 parts by weight of polyol A [branched polyether polyol (average hydroxyl value: 28 mg KOH / g, manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumifene 3063)], which is PPG having ethylene oxide added to the terminal. PPG type polymer polyol (average hydroxyl value: 28 mgKOH / g, manufactured by Sanyo Chemical Industries, Ltd., trade name: Sannix FA-728R)] 20 parts by weight, triethanolamine 1.5 parts by weight, 3.5 parts by weight of water as a blowing agent , Foaming agent [silicone-based foaming agent (manufactured by Nihon Unicar Co., Ltd., trade name: L-3601)] 0.5 parts by weight, communication agent [cell opener (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: additive) J225)] 1.5 parts by weight and a catalyst having the composition shown in Table 1 were mixed by a laboratory mixer to obtain a polyol mixture.
[0053]
The resulting polyol mixture and the isocyanate component [manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumidur 44V20] were mixed and stirred with a lab mixer at 15 ° C. so that the isocyanate index was 100, and the resulting mixture was obtained. 300 g was poured into a mold [inside dimension: 150 × 150 × 300 (height) mm] to mold a polyurethane foam free form.
[0054]
In addition, each abbreviation shown in Table 1 means the following.
(catalyst)
KL-25: 6-dimethylamino-1-hexanol (trade name: Kao Riser No. 25, manufactured by Kao Corporation)
KL-P200: Poly tertiary amine glycol [manufactured by Kao Corporation, trade name: Kaoraiza P200, in Formula (II), compound wherein R ¹ hexamethylene group, R ² is a methyl radical, n is 3.5]
KL-31: Dipropylene glycol solution of 33% triethylenediamine (manufactured by Kao Corporation, trade name: Kao Raiser No. 31)
TMAEEA: N, N, N'-trimethyl-N '-(2'-hydroxyethyl) -1,2-ethylenediamine TMAPEA: N, N, N'-trimethyl-N'-(2'-hydroxyethyl) -1 , 3-Propylenediamine [0055]
Next, the physical properties of the obtained polyurethane foam were examined according to the following method. The results are also shown in Table 1.
[0056]
1. Strength retention The strength retention is an index of heat resistance.
After the molded freeform is allowed to stand at room temperature for 24 hours, 10 test pieces for tensile test measurement of type 2 are cut out from the freeform in accordance with JIS K 6301, and 5 of them are pulled at room temperature. Average strength (initial strength) when the tensile test was performed at a pulling speed of 125 mm / min using a tester [Autograph manufactured by Shimadzu Corporation, product number: DCS-50M], and the remaining five test pieces The average value of the strength (strength at high temperature) when measured in the same manner as described above after being left in an atmosphere at 120 ° C. for 24 hours is calculated using the formula:
[Strength retention (%)] = [High-temperature strength] ÷ [Initial strength] x 100
Sought according to.
[0057]
2. After leaving the haze-molded free form for one day at room temperature, cut out a test piece (50mm x 50mm x 100mm) from the core and place it in a 500mL glass bottle containing 0.1mL of 2N hydrochloric acid. After sealing the opening with a transparent glass plate and immersing about two-thirds of this glass bottle in a hot water bath maintained at 80 ° C. for 100 hours, the haze value of the glass plate is measured with a haze meter (color difference meter). [Nippon Denshoku Industries Co., Ltd., product number: NDH-20D].
[0058]
The haze value is an index when VOC based on the amine catalyst is generated from the polyurethane foam, and the smaller the haze value, the lower the VOC and fogging at high temperatures.
[0059]
3. Free amine amount The free amine amount is an indicator of the amount of VOC generated from polyurethane foam based on amine catalysts.
[0060]
A test piece (50 mm x 50 mm x 50 mm) is cut out from the molded freeform, immersed in a 500 mL beaker containing 50 mL of ion-exchanged water, and the test piece is compressed 20 times with a push rod (surface area of 25 cm ² or more). The free amine catalyst was eluted in water.
[0061]
After removing the test piece from the beaker (at this time, sufficiently draining the water contained in the test piece and returning it to the beaker), weighed the amine-eluted water with a 25 mL hole pipette, put it in an Erlenmeyer flask, 0.01% Titrate with aqueous mol / L hydrochloric acid, correct the molecular weight of the catalyst from the titration of neutralization point, formula:
[Amount of free amine (mg / form 1L)]
= [(50/25) / (0.5 x 0.5 x 0.5)] x 0.01 x titer (mL)] x [molecular weight of catalyst]
The amount of free amine was determined according to
[0062]
4). Free-form core density After producing the free-form, leave it for one day, cut out a test piece of 100 mm x 100 mm x 100 mm from the core, measure the weight of the test piece, and divide it by its volume. Measured.
[0063]
5. Fluidity Fluidity is an indicator of moldability.
Adjust the mold temperature of the fluidity measurement mold 1 (made of aluminum) having the shape shown in FIG. 1 (a) to 60 ° C., then place each of the examples or comparative examples at point A in the mold 1 After casting 25 g of the mixture obtained in the above step, the top lid (not shown) was capped and molded, and after 6 minutes, the mold was removed and the polyurethane foam 2 shown in FIG. The length L was measured.
In addition, it shows that fluidity | liquidity is so favorable that the length of foam | foam is excellent and moldability is excellent.
[0064]
6). Curability (initial)
A polyurethane foam was molded by reacting 60 g of the mixture obtained in each Example or each Comparative Example in a 300 mL polycup [trade name: Death Cup, manufactured by Terraoka Co., Ltd.]. The state of the polyurethane foam overflowed from the polycup was observed, and the curability (initial) was evaluated based on the following evaluation criteria.
[0065]
〔Evaluation criteria〕
A: The polyurethane foam overflowing from the polycup stands almost vertically.
○: The polyurethane foam overflowing from the polycup is slightly swollen and stands vertically.
X: The polyurethane foam which overflowed from the polycup is dripping on the side surface of the polycup.
[0066]
7). Curability (late stage)
Forming polyurethane foam in the same way as when evaluating fluidity, removing the mold after 3 minutes, observing the state of the polyurethane foam part with a thickness of 5 mm, and curing (late) based on the following evaluation criteria Evaluated.
[0067]
〔Evaluation criteria〕
A: The polyurethane foam is not sticky and has good curability.
○: The polyurethane foam is slightly sticky, but the curability is almost satisfactory.
X: The polyurethane foam is sticky, the foam adheres to the mold during demolding, and the curability is insufficient.
[0068]
[Table 1]
[0069]
From the results shown in Table 1, according to each example, the amount of VOC based on the amine-based catalyst is reduced from the polyurethane foam even at a high temperature, making it difficult to generate fogging and heat resistance. It can be seen that a polyurethane foam excellent in curability and moldability can be produced even if the shape is good and the shape is wide and thin.
[0070]
【The invention's effect】
According to the present invention, even in a high temperature state, the amount of VOC based on an amine-based catalyst is reduced from polyurethane foam, making it difficult for fogging to occur, having good heat resistance, and having a wide thickness. Even if it is a thin shape, the effect that the polyurethane foam excellent in sclerosis | hardenability and moldability can be manufactured is show | played.
[Brief description of the drawings]
FIG. 1 (a) is a schematic explanatory diagram of a fluidity measurement mold used in examining fluidity in each example or comparative example of the present invention, and (b) uses the fluidity measurement mold. It is a schematic perspective view of the polyurethane foam shape | molded by this.
[Explanation of symbols]
1 Mold for measuring fluidity 2 Polyurethane foam

Claims (4)

Formula (I):
(CH ₃ ) ₂ N (CH ₂ ) _p OH (I)
(Wherein p represents an integer of 4 to 9)
And a compound represented by formula (II):
HO- [R ¹ -N (R ² )] _N -R ¹ -OH (II)
[Wherein R ¹ Are the same or different C2-C24 linear or branched alkylene group, alicyclic alkylene group, cycloalkylene group, aralkylene group or formula:
(Wherein R ³ Is a hydrogen atom or a methyl group, R ⁴ Are the same or different linear or branched alkylene groups having 2 to 24 carbon atoms, alicyclic alkylene groups, cycloalkylene groups or aralkylene groups, x is the average degree of polymerization and represents a number of 0 to 15)
A group represented by R ² Are the same or different linear or branched alkyl groups or aralkyl groups having 1 to 9 carbon atoms, n is the average degree of polymerization, and represents a number of 2 to 50.
A process for producing a polyurethane foam in which a polyol component and an isocyanate component are reacted in the presence of a catalyst containing a compound represented by formula (I) and a foaming agent comprising water , wherein the polyurethane foam is represented by the formula (I). The total weight of the compound represented by formula (II) and the compound represented by formula (II) 0.3 parts by weight -5 parts by weight and the weight ratio of the compound represented by the formula (I) to the compound represented by the formula (II) (the compound represented by the formula (I) / the formula (II) Compound) is 30/70 ~ 80/20 A method for producing polyurethane foam .   The process according to claim 1, wherein the compound represented by the formula (I) is 6-dimethylamino-1-hexanol. In the compound represented by the formula (II), R ¹ Is a linear or branched alkylene group having 2 to 9 carbon atoms, R ² The production method according to claim 1 or 2, wherein is a linear or branched alkyl group having 1 to 4 carbon atoms, and n is a positive number having 2 to 10. The polyurethane foam obtained by the manufacturing method in any one of Claims 1-3 .