Process for the production of flexible polyurethane foams

专利摘要:
PURPOSE: A method for preparing a flexible polyurethane foam is provided, to obtain a polyurethane foam having an excellent formability and a high ventilating property by reacting polyol and polyisocyanate without using a tin-based catalyst. CONSTITUTION: The method comprises the step of reacting polyol and polyisocyanate in the presence of a catalyst, wherein the polyol contains at least one 5 wt% of oxyethylene groups inside of the chain (based on the weight of total polyol) and is terminal-capped with a secondary OH group; the polyisocyanate is toluene diisocyanate and/or its derivative; and the catalyst is at least one selected from the imidazole compounds represented by the formula 1. In the formula 1, R1, R2 and R3 are independently H, an alkyl group of C1-C4, a hydroxymethyl group or a phenyl group; R4 is H, an alkyl group of C1-C4, an aminopropyl group, a dimethylaminopropyl group, a benzyl group, a vinyl group, an aryl group, a benzyl group, a phenyl group, a cyanoethyl group or a functional group represented by the formula A, wherein R5 is H or an alkyl group of C1-C4; and p is an integer of 1-3. The method does not use a tin-based catalyst.
公开号:KR20030036060A
申请号:KR1020020066607
申请日:2002-10-30
公开日:2003-05-09
发明作者:코메타니히로유키；타마노유타카
申请人:토소가부시키가이샤；
IPC主号:

专利说明:

Manufacturing method of flexible polyurethane foam {PROCESS FOR THE PRODUCTION OF FLEXIBLE POLYURETHANE FOAMS}
[1] The present invention relates to a method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and other auxiliaries. In particular, the present invention relates to a method for producing a flexible polyurethane foam, characterized in that no tin-based catalyst is used.
[2] Polyurethanes are prepared by reacting a polyisocyanate with an organic polyol in the presence of a catalyst and, if necessary, other adjuvants, such as blowing agents, surfactants, and, optionally, crosslinking agents. Among them, flexible polyurethane foams are widely used in products such as vehicles, furniture, bedding, and cushions because of their light weight and excellent elasticity. Among the flexible polyurethane foam, hot mold form is mainly used in the automobile seat cushion field, and slab foam is mainly used in the furniture, bedding, and cushion field.
[3] Generally, in slab foam and hot mold foam, a good foam is produced by using a tin catalyst and an amine catalyst as catalysts. In particular, the use of a tin catalyst is indispensable from the viewpoint of curability and molding process. As the tin-based catalyst, stannous dioctoate, dibutyltin dilaurate and the like are generally used. As the polyol, a low-cost general-purpose polyol in which propylene oxide (hereinafter referred to as PO) is added to glycerin as an initiator is generally used. In previous low density foam manufacturing, freon compounds such as CFC-11 have been used as blowing agents. However, it is pointed out that freon compounds destroy the ozone layer, and strict freon regulations are enforced worldwide. Therefore, in recent years, the method of using methylene chloride and water as a substitute for a freon compound has been adopted. However, adverse effects on the environment and its toxicity have also been noted for methylene chloride. Therefore, a method of using only water as a blowing agent or a method of using carbon dioxide as a blowing agent has been proposed.
[4] In addition to the improvement of the blowing agent, in recent years, improvement in the catalyst system has also been required. That is, a small amount of dibutyltin, etc., which is highly toxic, is mixed in the tin catalyst as impurities, and this impurity cannot be removed. Therefore, it is pointed out that the use of tin catalysts leaves highly toxic chemicals in urethane foams. In addition to the toxicity problem, tin-based catalysts have been pointed out that the storage stability in the premix is poor, and long-term storage is difficult. Due to these problems, there is a strong demand for the development of a prescription capable of producing slab foam or hot mold foam without using a tin catalyst.
[5] In conventional formulations, the use of a general purpose tertiary amine catalyst such as triethylenediamine and N-ethyl morpholine in combination with a tin catalyst has been generally performed. However, the above-mentioned tertiary amine catalyst and the like remain in the free form in the polyurethane resin product and are gradually discharged as volatile amines, causing various problems. For example, volatile amines emitted from polyurethane foam products cause odor problems. Moreover, in recent years, volatile components in polyurethane foam adhere to windshields of automobiles and blur the windshields, resulting in a decrease in product value. In addition, there are other problems, such as problems with other materials by volatile amines emitted from polyurethane products. Therefore, improvement is also required in the above-mentioned problem which arises when using a general-purpose catalyst.
[6] However, in the conventional polyol, the tin catalyst is removed from the conventional formulation using a general-purpose polyol (polyol obtained by adding PO to glycerin), and triethyleneamine, N, N-dimethylaminoethanol, and the like, which are conventionally used, and When a flexible polyurethane foam is formed with a general-purpose amine catalyst such as N-ethyl morpholine, foam formation becomes unstable, deforming (foam collapse), or cracks may be formed even if the foam can be formed. Serious problems such as occurrence or insufficient air permeability have arisen, and a foam excellent in physical properties cannot be obtained.
[7] Instead of the conventional polyol, there is also a method of using a highly reactive polyol having an oxyethylene group introduced at the terminal of the polyol chain. In this case, there is a problem that the ratio of independent bubbles in the foam is increased. As a result, there is a problem that the air permeability of the foam is significantly deteriorated and the shrinkage of the foam occurs.
[8] In addition, in order to solve the odor problem and the fogging problem caused by the general purpose amine catalyst, a method using a so-called reactive catalyst containing an amine group or a hydroxyalkyl group in its molecule has been proposed. However, when the tin-based amine catalyst is removed from the conventional formulation and the foam is formed only by the reactive catalyst, the molding of the foam becomes more unstable than when only the universal catalyst is used, and thus a good foam cannot be obtained. In addition, some amine catalysts may volatilize from a foam among reactive catalysts. Therefore, without using an appropriate reactive amine catalyst, odor problems and fogging problems cannot be solved.
[9] Under this background, it is an object of the present invention to solve the above-mentioned problems associated with the prior art, to provide a flexible polyurethane foam without using a tin catalyst.
[10] Therefore, as a result of extensive and intensive studies on the formulation of a flexible polyurethane foam without using a tin catalyst, when the amine compound having a specific polyol and a specific chemical structure is used as a catalyst, the formability of the foam is excellent and high. It has been found that the production of breathable flexible polyurethane foams is possible, and that the urethane foam products produced by the third embodiment of the present invention described below do not cause odor problems and fogging problems. The present invention has been completed based on this finding.
[11] In particular, the present invention includes the following three embodiments.
[12] 1. A first embodiment of the present invention relates to a method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a blowing agent.
[13] (1) As a polyol, using a polyether polyol containing at least 5% by weight or more of oxyethylene groups (relative to the weight of the total polyol) in the chain and whose ends are sealed with secondary OH groups,
[14] (2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
[15] (3) As the catalyst, one or two or more compounds selected from the imidazole compounds represented by the following chemical formulas are used,
[16] [Formula]
[17]
[18] Wherein R 1, R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydroxymethyl group or a phenyl group; R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an aminopropyl group or dimethylamino A propyl group, benzyl group, vinyl group, aryl group, benzyl group, phenyl group, cyanoethyl group or a functional group represented by the following formula,
[19] [Formula]
[20]
[21] (Herein, R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3.) A tin catalyst is not used.
[22] 2. A second embodiment of the present invention relates to a method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst, which method
[23] (1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol At least 5% by weight or more of the polyol chain terminal is used in combination with a polyether polyol (B) which is a primary OH group,
[24] (2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
[25] (3) As the catalyst, one or two or more selected from the group consisting of an imidazole compound represented by the following chemical formula, triethylenediamine and N-methyl-N '-(2-dimethylaminoethyl) piperazine Use,
[26] [Formula]
[27]
[28] (Wherein R 1, R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group; R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a vinyl group, an aryl group, A phenyl group and a cyanoethyl group.),
[29] (4) It is characterized by not using a tin catalyst.
[30] 3. The third embodiment of the present invention relates to a method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst, which method
[31] (1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol To polyether polyol (B), wherein at least 5% by weight or more of the polyol chain ends are used as primary OH groups, and the ratio of polyether polyol (A) to polyether polyol (B) is based on 10 / 90-90 / 10,
[32] (2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
[33] (3) A compound represented by the following formula (1) as a catalyst:
[34] [Formula 1]
[35]
[36] Wherein R 1, R 2, and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a phenyl group, a benzyl group, a vinyl group, an allyl group, or a cyanoethyl group; R 4 is an amino propyl group , A dimethylaminopropyl group, or a substituent represented by the following formula,
[37] [Formula]
[38]
[39] Here, R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3.)
[40] Compound represented by the following formula (2):
[41] [Formula 2]
[42]
[43] Wherein R 6 and R 7 independently represent an alkyl group having 1 to 4 carbon atoms, a dimethylaminopropyl group or a diethylaminopropyl group, and R 6 and R 7 are each bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R8 represents an alkylene group having 2 to 16 carbon atoms.
[44] Compound represented by the following formula (3):
[45] [Formula 3]
[46]
[47] Herein, R9 and R10 independently represent an alkyl group having 1 to 4 carbon atoms, dimethylaminopropyl group or diethylaminopropyl group, and R9 and R10 may be bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R 11 represents an alkylene group having 3 to 16 carbon atoms, R 12 represents an alkylene group having 2 to 3 carbon atoms, m 1 represents an integer of 0 to 2, R 13 represents an alkyl group having 1 to 4 carbon atoms, or the following: A substituent represented by the chemical formula of
[48] [Formula]
[49]
[50] Here, R12 and m1 are defined as above.)
[51] Compound represented by the following formula (4):
[52] [Formula 4]
[53]
[54] (In this case, R14 and R15 independently represent an alkyl group having 1 to 4 carbon atoms, dimethylaminopropyl group or diethylaminopropyl group, and R14 and R15 may be bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R16 represents an alkylene group having 3 to 16 carbon atoms.
[55] Compound represented by the following formula (5):
[56] [Formula 5]
[57]
[58] (R 17, R 18, and R 19 independently represent an alkyl group having 1 to 4 carbon atoms, R 20 represents a hydrogen atom or a methyl group, and m 2 represents an integer of 1 to 3.)
[59] In addition, using one or two or more compounds selected from the group consisting of compounds represented by the following formula (6),
[60] [Formula 6]
[61]
[62] (Herein, R21, R22, and R23 represent an alkyl group having 1 to 4 carbon atoms; R24 represents a hydrogen atom or a methyl group; m3 and n represent an integer of 1 to 3.)
[63] (4) It is characterized by not using a tin catalyst.
[64] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
[65] In the method of the present invention, an imidazole compound represented by the following chemical formula is used as a catalyst,
[66] [Formula]
[67]
[68] Wherein R 1, R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydroxymethyl group or a phenyl group; R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an aminopropyl group or dimethyl group; Aminopropyl group, benzyl group, vinyl group, aryl group, benzyl group, phenyl group, cyanoethyl group, or a functional group represented by the following formula,
[69] [Formula]
[70]
[71] Here, R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3). Examples of the imidazole compound are 1,2-dimethylimidazole and 1-methylimide. Sol, 1,4-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 1-methyl-2-isopropylimidazole, 1-methyl-2-phenylimidazole, 1- (n-butyl) -2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-vinylimidazole, 1-benzyl-2-methylimidazole, imidazole, 2-methyldi Midazole, 1- (2'-hydroxypropyl) -imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) -imidazole, 1 -(2'-hydroxyethyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (3'-aminopropyl) -2-methylimidazole, 1- ( 3'-dimethylaminopropyl) -imidazole, 1- (3'-hydroxypropyl) -imidazole, and 1- (3'-hydroxypropyl) -2-methylimidazole, among which 1, 2-dimethylimidazole, 1-methylimida Sol, 1-n-butyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1- (3'-dimethylaminopropyl) -imidazole, 1- (3'-hydroxypropyl ) -2-methylimidazole, 1- (3'-hydroxypropyl) -imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl ) -Imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, and 1- (2'-hydroxyethyl) -imidazole have high catalytic activity and are used industrially advantageously. In the method of this invention, these imidazole compounds can be used individually or in mixture of 2 or more types.
[72] You may dilute these catalysts with a solvent as needed. The solvent is not particularly limited as long as it is commonly used. Examples of the solvent include dipropylene glycol, ethylene glycol, 1,4-butanediol, diethylene glycol, and water.
[73] The amount of the catalyst used is usually 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight of polyol.
[74] In the method of the present invention, other tertiary amines can be used in combination as long as the function of the present invention is not impaired. Such tertiary amine catalyst is not particularly limited and may be used as long as it is known in the art. Examples of tertiary amine catalysts used are 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 "-pentamethyldi Propylenetriamine, N, N, N ', N'-tetramethylganidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-s-triazine, 1,8-diazabi Cyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, and bis (2-dimethylaminoethyl) ether.
[75] The process according to the invention is characterized in that no tin-based catalyst is used as catalyst. In particular, as mentioned in the present invention, tin-based catalysts are catalysts for the production of flexible polyurethane foams, and include tinner's diacetate, strainer dioctoate, tinner's dioleate, tinner's dilaurate and dibutyltin oxide. And commonly known organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate.
[76] The polyols used in the process according to the invention are polyether polyols which contain at least 5% by weight or more of oxyethylene groups inside the chain and which have terminal OH groups. Such polyether polyols include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimetholpropane, and pentaerythritol as initiators, and include ethylene oxide (hereinafter referred to as EO) and propylene oxide ( By addition polymerization of alkylene oxides represented by PO), for example, as described in pages 42-53 of Gunter Oertel, "Polyurethane Hnadbook" (1985), published by Hanser Plblishers (Germany) It can manufacture by.
[77] Examples of addition polymerization of propylene oxide and ethylene oxide include: (a) a triblock copolymer reaction in which addition polymerization of propylene oxide is followed by addition polymerization of ethylene oxide, followed by addition polymerization of propylene oxide; And (b) a copolymerization reaction which further polymerizes propylene oxide after random reaction of random copolymerization of propylene oxide and ethylene oxide. In the method according to the present invention, any method may be used. When addition-polymerizing an epoxide compound, it is also possible to use a basic catalyst. Examples of the timing of introducing the catalyst include: (a) a method of adding a catalyst simultaneously with the polyhydric alcohols as the initiator and performing addition polymerization of the epoxide compound; And (b) a method in which a catalyst is added after the polyhydric alcohols as an initiator and the epoxide compound are reacted without a catalyst, and further addition polymerization of the epoxide compound is carried out.
[78] In the method according to the present invention, any of these methods can be used.
[79] Examples of the basic catalyst include alkali metal compounds, alkaline earth metal compounds, and amine compounds. Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide; And carbonates of alkali metals or alkaline earth metals such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. Moreover, hydrogencarbonate, such as potassium hydrogencarbonate and sodium hydrogencarbonate, can also be used. Examples of amine compounds include triethylamine, dimethylethanolamine, pyridine, methyldimethylamine, tri-n-propylamine, dimethylpalmitylamine, dimethyloctylamine, and the like. These catalysts can be used alone or as a mixture of two or more thereof.
[80] In the method according to the present invention, as described above, the polyol is prepared, and then usually subjected to post-treatment to remove the basic catalyst used. Examples of the post-treatment method include (a) at least one neutralizing agent selected from inorganic acids (such as hydrochloric acid, phosphoric acid and lactic acid), organic acids (such as formic acid, acetic acid, fish acid, succinic acid, phthalic acid and maleic acid) and carbon dioxide. Neutralization method; (b) a method of treating with an ion exchange resin; And (c) a method of treating with an adsorbent. The polyol may also be purified using water, a solvent inert to the polyol, or a mixture of water and a solvent.
[81] In the process according to the invention, polyether polyols prepared with glycerine or trimethiololpropane as an initiator and addition of EO and PO are particularly preferred. However, the addition position of EO and PO may be random in the polyol chain, the addition to the terminal may allow only PO, and the addition ratio of EO and PO is 5 wt% or more of EO. The molecular weight of the polyether polyol is usually in the range of 1,500 to 7,000, preferably in the range of 2,000 to 5,000. When this is represented by the hydroxyl value, a hydroxyl value is normally the range of 24-112 mgKOH / g, Preferably it is the range of 33-84 mgKOH / g.
[82] In the process according to the invention, the choice of polyols is important. For example, in the case of using a general-purpose polyol obtained by adding only PO to glycerin, problems such as deforming and significantly impaired breathability occur. In addition, even when an imidazole catalyst is used in the present invention, the air permeability of the foam is deteriorated, and a good foam cannot be formed.
[83] Moreover, when EO is added to the terminal part and the polyol sealed by the terminal primary OH group is used, the problem that the ratio of independent bubbles in a foam becomes high arises. As a result, the air permeability of the foam is remarkably deteriorated, and shrinkage of the foam may occur in some cases. Moreover, even if it uses the imidazole series catalyst of this invention, it is difficult to improve air permeability and a favorable foam cannot be formed.
[84] In addition, even when a polyol is used in the present invention, when an amine catalyst other than the catalyst of the present invention is used, there is a problem that deforming occurs, cracks are generated in the foam, or the foam surface is broken and peeled off, thereby forming a good foam. Can not.
[85] The polyisocyanate used in the present invention is toluene diisocyanate (hereinafter referred to as TDI) and / or a derivative thereof. Examples of TDI include 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and mixtures thereof. Derivatives of TDI are, for example, terminal isocyanate prepolymer derivatives. In the manufacture of the flexible foam of the present invention, a mixture of 2,4-toluene diisocyanate and 2,6-toluene isocyanate which can be easily obtained industrially can be preferably used.
[86] In the process according to the invention, the isocyanate index (isocyanate group / active hydrogen group which can react with this isocyanate group) is not particularly limited, but is generally in the range of 60 to 130.
[87] Water and / or carbon dioxide is preferred as the blowing agent used in the present invention, and it is also possible to use halogenated hydrocarbons as blowing agents. Examples of halogenated hydrocarbons include methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichlorotrifluoromethane, dichloromonofluoromethane, 1,1,1,2-tetrafluoroethane, 1,1- Conventional halogenated methanes, halogenated ethanes, such as dichloro-1-fluoroethane, 1,1,3,3,3-pentafluoropropane and 2,2,4,4,4-pentafluoropropane. Foaming agents are particularly preferred water. The amount of water used may vary depending on the density of the desired foam, but is usually 2 parts by weight or more per 100 parts by weight of polyol, preferably 2 to 8 parts by weight, and more preferably 3 to 5.5 parts by weight. If the amount of water is less than 2 parts by weight, the foaming ratio is extremely low, and a low density foam cannot be formed. On the contrary, when the amount of water is 8 parts by weight or more, foaming becomes unstable, and deforming is likely to occur, thereby causing problems such as the inability to form foam or the generation of scorch.
[88] In the process according to the invention, if necessary, auxiliaries such as foam stabilizers, crosslinkers or chain extenders, colorants, flame retardants, antioxidants and the like can be used.
[89] In the process according to the invention, foam stabilizers can be used if necessary. This foam stabilizer can use conventional organic silicone surfactants in the present invention. The amount of foam stabilizer to be used is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of polyol.
[90] In the process according to the invention, crosslinking agents or chain extenders can be used if necessary. Examples of crosslinking agents or chain extenders include low molecular weight polyhydric alcohols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and glycerin; And polyamines such as ethylenediamine, xylenediamine and methylene bis-o-chloroaniline. Among these, diethanolamine and triethanolamine are preferable.
[91] In the method according to the present invention, colorants, flame retardants, antioxidants, other conventional additives, and the like may also be used, if necessary. Examples of the flame retardant include, but are not limited to, chloroalkyl phosphate, dimethylmethyl phosphate, polymeric phosphate, bromine-phosphate, organic bromine compound, ammonium polyphosphate, diethyl phosphate, bishydroxyethyl phosphate, aminoethyl phosphate, Neopentylpromide adipate, dibromopropanol, dibromoneopentyl glycol, brominated polyethers, and the like. The kind and addition amount of these additives can fully be used in the range normally used, without deviating from a normal form and procedure.
[92] Next, a second embodiment of the present invention will be described in detail. The catalyst used in the process according to the invention is an imidazole compound represented by the following formula,
[93] [Formula]
[94]
[95] (Wherein R 1, R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group; R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a vinyl group, an aryl group, Phenyl group or cyanoethyl group), triethylenediamine, and at least one compound selected from the group consisting of N-methyl-N '-(2-dimethylaminoethyl) piperazine. Examples of the imidazole compound represented by Formula 1 include 1,2-dimethylimidazole, 1-methylimidazole, 1,4-dimethylimidazole, 1,2,4,5-tetramethylimidazole , 1-methyl-2-isopropylimidazole, 1-methyl-2-phenylimidazole, 1- (n-butyl) -2-methylimidazole, 1-isobutyl-2-methylimidazole , 1-vinylimidazole, 1-benzyl-2-methylimidazole, imidazole, and 2-methylimidazole. Of course, 1,2-dimethylimidazole, 1-methylimidazole, 1-n-butyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole have high catalytic activity Industrially advantageously used. These catalysts are usually used alone, respectively, but may be used as a mixture of two or more thereof.
[96] In addition, in this invention, catalysts other than the catalyst of this invention mentioned above can be combined and used within the range which does not lose the function of this invention. Examples of other catalysts include metal catalysts and amine catalysts except tin catalysts. Of course, amine catalysts having a high reaction activity between water and isocyanate are preferred, and bis (2-dimethylaminoethyl) ether and pentamethyldiethylenetriamine are particularly preferred.
[97] If necessary, these catalysts may be diluted with a solvent and used. The solvent is not particularly limited as long as it is usually used. Examples of the solvent include dipropylene glycol, ethylene glycol, 1,4-butanediol, diethylene glycol, and water.
[98] The use amount of these catalysts is 100 parts by weight of polyol, and usually 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight.
[99] The process according to the invention is characterized in that no tin-based catalyst is used as catalyst. Specifically, the tin-based catalyst used in the present invention is a stanus diacetate, a stanus dioctoate, a stanus dioleate, a stanus dilaurate, a dibutyltin oxide, a dibutyltin diacetate, a dibutyltin di Conventional organic tin compounds, such as laurate, dibutyltin dichloride, and dioctyltin dilaurate.
[100] The process according to the invention comprises at least 5% by weight or more of oxyethylene groups inside the polyol chain, wherein the polyether polyol (A) having a terminal secondary OH group and at least 5% of the polyol chain ends are primary OH groups It is characterized by using a polyether polyol (B).
[101] As the polyether polyol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol are used as the initiators, and ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as "polyethylene polyol"). By addition polymerization of alkylene oxides represented by, for example, by the method described in Gunter Oertel "Polyuretnane Handbook (1985), pages 42-53, published by Hanser Publishers (Germany). Examples of the addition polymerization reaction of PO and EO include (a) addition polymerization of EO after addition polymerization of PO, further block copolymerization reaction of addition polymerization of PO and EO, and (b) PO. Copolymerization reaction of addition polymerization of PO is further included after the random reaction which copolymerizes and EO randomly, Any of these methods can be used.
[102] When addition polymerization of an epoxide compound, it is also possible to use a basic catalyst. As an example of the timing of the catalyst input,
[103] (a) the method of adding a catalyst simultaneously with the polyhydric alcohol which is an initiator, and performing addition polymerization of an epoxide compound; And
[104] and (b) a method in which a catalyst is added after the polyhydric alcohols as the initiator and the epoxide compound are reacted without a catalyst, and the addition polymerization of the epoxide compound is further performed.
[105] Any of these methods can be used. Examples of basic catalysts include alkali metal compounds, alkaline earth metal compounds, amine compounds. Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide; And carbonates of alkali metals or alkaline earth metals such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. Moreover, hydrogencarbonate, such as potassium hydrogencarbonate and sodium hydrogencarbonate, can also be used. Examples of the amine compound include triethylamine, dimethylethanolamine, pyridine, tridimethylamine, tri-n-propylamine, dimethylpalmitylamine, dimethyloctylamine, and the like. These catalysts can be used alone or as a mixture of two or more thereof.
[106] After preparing a polyol as described above, it is usually post-treated to remove the used basic catalyst. Examples of post-processing methods are
[107] (a) neutralization treatment with at least one neutralizing agent selected from inorganic acids (such as hydrochloric acid, phosphoric acid, lactic acid), organic acids (such as formic acid, acetic acid, oxalic acid, succinic acid, phthalic acid, maleic acid) and carbon dioxide;
[108] (b) a method of treating with an ion exchange resin; And
[109] (c) a method of treating with an adsorbent.
[110] The polyol may also be purified using water, a solvent inert to the polyol, or a mixture of water and a solvent.
[111] The polyol is particularly preferably a polyether polyol prepared by using glycerine or trimethiololpropane as an initiator and adding EO and PO. However, the addition position of EO and PO may be random in the polyol chain, the addition to the terminal may allow only PO, and the addition ratio of EO and PO is 5 wt% or more of EO. The molecular weight of the polyether polyol is usually in the range of 1,500 to 7,000, preferably in the range of 2,000 to 5,000. When this is represented by the hydroxyl value, a hydroxyl value is normally the range of 24-112 mgKOH / g, Preferably it is the range of 33-84 mgKOH / g.
[112] In the process according to the invention, the choice of polyols is important. For example, in the case of using a general-purpose polyol obtained by adding only PO to glycerin, problems such as deforming and significantly impaired breathability occur. Moreover, even if the catalyst of the present invention is used, the air permeability of the foam is deteriorated, and a good foam cannot be formed.
[113] When using only the polyether polyol (A) of this invention as a polyol independently, it is difficult to form a low density foam. In addition, when a conventional amine catalyst is used, there is a problem that deforming occurs, cracks are generated in the foam, or the surface of the foam is broken and peeled off, whereby a good foam cannot be formed.
[114] When only the polyether polyol (B) of the present invention is used alone as a polyol, there is a problem that the proportion of free bubbles in the foam is increased. As a result, the breathability of the foam may be significantly deteriorated and shrinkage of the foam may occur. Moreover, even if the catalyst of the present invention is used, it is difficult to improve breathability, and thus a good foam cannot be formed.
[115] As a polyol, even if the polyether polyol (A) of this invention and general purpose polyol obtained by adding only PO to glycerin are combined, serious problems, such as deforming and breathability deteriorate significantly, arise. Moreover, even if the catalyst of the present invention is used, the air permeability of the foam is deteriorated, and a good foam cannot be formed. Similarly, even if the polyether polyol (B) of the present invention is used in combination with a general-purpose polyol obtained by adding only PO to glycerin, serious problems such as deforming and poor air permeability are caused. In addition, even if the catalyst of the present invention is used, the air permeability of the foam is deteriorated, and a good foam cannot be formed. That is, by using the polyether polyol (A) and polyether polyol (B) of the present invention in combination, and using the catalyst of the present invention, it is possible to form a good foam without using a tin catalyst.
[116] Although the use ratio of the polyether polyol (A) and the polyether polyol (B) of the present invention is not limited, it is 10/90 to 90/10 in weight percent ratio, preferably 20/80 to 80/20, more preferably It is 30/70 ~ 70/30. If the use ratio of the polyether polyol (A) is too high, cracks are likely to occur, and the foam density is increased. On the contrary, when the use ratio of the polyether polyol (B) is too high, the air permeability of the foam is deteriorated.
[117] In addition, even when the polyether polyol (A) and the polyether polyol (B) of the present invention are used in combination, when an amine catalyst other than the catalyst of the present invention is used, deforming occurs, cracks are generated in the foam, There is a problem that the foam surface is broken and peeled off, and a good foam cannot be formed.
[118] The polyisocyanate used in the present invention is toluene diisocyanate (hereinafter referred to as "TDI") and / or derivatives thereof. Examples of TDI include 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and mixtures thereof. Derivatives of TDI are, for example, terminal isocyanate prepolymer derivatives. In the manufacture of the flexible foam of the present invention, a mixture of 2,4-toluene diisocyanate and 2,6-toluene isocyanate which can be easily obtained industrially can be preferably used.
[119] In the process according to the invention, the isocyanate index (isocyanate group / active hydrogen group which can react with this isocyanate group) is not particularly limited, but is generally in the range of 60 to 130.
[120] In the method according to the present invention, auxiliary agents such as foaming agents, foam stabilizers, crosslinking agents or chain extenders, colorants, flame retardants, and antioxidants can be used as necessary.
[121] As the blowing agent used in the present invention, water and / or carbon dioxide is preferable. It is also possible to use a halogenated hydrocarbon as a blowing agent. Examples of halogenated hydrocarbons include methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichlorotrifluoroethane, dichloromonofluoromethane, 1,1,1,2-tetrafluorouroethane, 1,1 Conventional halogenated methanes, halogenated ethanes, such as dichloro-1-fluoroethane, 1,1,3,3,3-pentafluoropropane and 2,2,4,4,4-pentafluoropropane . Foaming agents are particularly preferred water. The amount of water used may vary depending on the density of the desired foam, but is usually 0.5 parts by weight or more per 100 parts by weight of polyol, preferably 0.5 to 8 parts by weight, and more preferably 2 to 5.5 parts by weight. If the amount of water is less than 0.5 parts by weight, the foaming ratio is extremely low, and a low density foam cannot be formed. On the contrary, when the amount of water is 8 parts by weight or more, foaming becomes unstable and deforming is likely to occur, thereby causing problems such as the inability to form a foam or the occurrence of scorch.
[122] In the process according to the invention, foam stabilizers can be used if necessary. This foam stabilizer can use, for example, conventional organic silicone surfactants in the present invention. The amount of foam stabilizer to be used is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of polyol.
[123] In the process according to the invention, crosslinking agents or chain extenders can be used if necessary. Examples of crosslinking agents or chain extenders include low molecular weight polyhydric alcohols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and glycerin; And polyamines such as ethylenediamine, xylenediamine and methylene bis-o-chloroaniline. Among these, diethanolamine and triethanolamine are preferable.
[124] In the method according to the present invention, colorants, flame retardants, antioxidants, other conventional additives, and the like may also be used, if necessary. Examples of the flame retardant include, but are not limited to, chloroalkyl phosphate, dimethylmethyl phosphate, polymeric phosphate, bromine-phosphate, organic bromine compound, ammonium polyphosphate, diethyl phosphate, bishydroxyethyl phosphate, aminoethyl phosphate, Neopentylpromide adipate, dibromopropanol, dibromoneopentyl glycol, brominated polyethers, and the like. The kind and addition amount of these additives can fully be used in the range normally used, without deviating from a normal form and procedure.
[125] Next, a third embodiment of the present invention will be described in detail.
[126] The catalyst used in the process according to the present invention contains at least one primary amino group, secondary amino group or hydroxyalkyl group in a molecule, and is an amine compound represented by the following formulas (1) to (6).
[127] [Formula 1]
[128]
[129] Wherein R 1, R 2, and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a phenyl group, a benzyl group, a vinyl group, an aryl group, or a cyanoethyl group; R 4 is an amino propyl group , A dimethylaminopropyl group, or a substituent represented by the following formula,
[130] [Formula]
[131]
[132] Here, R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3.)
[133] Compound represented by the following formula (2):
[134] [Formula 2]
[135]
[136] Wherein R 6 and R 7 independently represent an alkyl group having 1 to 4 carbon atoms, a dimethylaminopropyl group or a diethylaminopropyl group, and R 6 and R 7 are each bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. Or R8 represents an alkylene group having 2 to 16 carbon atoms.)
[137] Compound represented by the following formula (3):
[138] [Formula 3]
[139]
[140] Herein, R9 and R10 independently represent an alkyl group having 1 to 4 carbon atoms, dimethylaminopropyl group or diethylaminopropyl group, and R9 and R10 may be bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. may or; R11 represents an alkylene group of a carbon atom number 3 ~ 16; R12 represents an alkylene group of carbon atoms 2 ~ 3, m1 is an integer of 0 ~ 2; R13 is to or an alkyl group of carbon atoms from 1 to 4 A substituent represented by the chemical formula of
[141] [Formula]
[142]
[143] Here, R12 and m1 are defined as above.)
[144] Compound represented by the following formula (4):
[145] [Formula 4]
[146]
[147] (In this case, R14 and R15 independently represent an alkyl group having 1 to 4 carbon atoms, dimethylaminopropyl group or diethylaminopropyl group, and R14 and R15 may be bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R16 represents an alkylene group having 3 to 16 carbon atoms.
[148] Compound represented by the following formula (5):
[149] [Formula 5]
[150]
[151] (Herein, R17, R18, and R19 independently represent an alkyl group having 1 to 4 carbon atoms, R20 represents a hydrogen atom or a methyl group, and m2 represents an integer of 1-3.)
[152] In addition, using one or two or more compounds selected from the group consisting of compounds represented by the following formula (6),
[153] [Formula 6]
[154]
[155] (Herein, R21, R22, and R23 represent an alkyl group having 1 to 4 carbon atoms; R24 represents a hydrogen atom or a methyl group; m3 and n represent an integer of 1 to 3.)
[156] An amine compound containing at least one primary amino group, secondary amino group, or hydroxyalkyl group in a molecule is usually called a reactive catalyst and is introduced into the resin skeleton by reacting with a polyisocyanate in the reaction of forming a flexible polyurethane foam. Volatilization of the catalyst from the foam is suppressed.
[157] In the method according to the present invention, it is important to use one or two or more compounds selected from the group consisting of amine compounds represented by the general formulas (1) to (6) among the reactive catalysts. By using the above catalyst, volatilization of the catalyst from the urethane foam is greatly suppressed, and good urethane foam can be formed.
[158] Among the reactive catalysts, when one or two or more compounds selected from the group consisting of the amine compounds represented by the formulas (1) to (6) are not used, the resulting foam can be deformed or good breathability can be obtained. If not, there is a fear that the scorch phenomenon that the inside of the foam is discolored red.
[159] In the method according to the present invention, examples of the imidazole compound represented by the formula (1) include 1- (2'-hydroxypropyl) -imidazole and 1- (2'-hydroxypropyl) -2- Methylimidazole, 1- (2'-hydroxyethyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (3'-aminopropyl) -2-methylimidazole, 1- (3'-hydroxypropyl) -imidazole and 1- (3'-hydroxypropyl) -2-methylimidazole . Among them, 1- (3'-aminopropyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, 1- (2'-hydroxypropyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, and 1- (2'-hydroxyethyl) -imidazole have high catalytic activity It is advantageously used industrially.
[160] In the method according to the present invention, the amine compound represented by the general formula (1) has at least one primary amino and tertiary amino group in the molecule. Examples of such amine compounds are N, N-dimethylethylenediamine, N, N-dimethylpropanediamine, N, N-dimethylbutanediamine, N, N-dimethylpentanediamine, N, N-dimethyl neopentanediamine, N, N -Dimethylhexanediamine, N, N-dimethylhexadecyldiamine, N, N-diethylethylenediamine, N, N-diethylpropanediamine, 4-amino-1-diethylaminopentane, N, N-diethylhexane Diamine, N- (aminoethyl) piperidine, N- (aminoethyl) -N'-methylpiperazine, N- (aminoethyl) morpholine, N- (aminopropyl) pyrrolidine, N- (aminopropyl ) -N'-methylpiperazine, N- (aminopropyl) morpholine, N, N-bis (dimethylaminopropyl) ethylenediamine, N, N-bis (dimethylaminopropyl) propanediamine, and N, N-bis (Diethylaminopropyl) propanediamine. Among them, N, N-dimethylethylenediamine, N, N-dimethylpropanediamine, N, N-dimethylbutanediamine, N, N-dimethylpentanediamine, N, N-dimethyl neopentanediamine, N, N-dimethylhexane Diamine, N- (aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) ethylenediamine, and N, N-bis (dimethylaminopropyl) propanediamine are more preferred because of their high catalytic reactivity.
[161] In the method according to the present invention, the amine compound represented by the formula (3) is a tertiary amine compound having at least one hydroxyalkyl group, and the ethylene jade group of the primary amine group of the amine compound represented by the formula (2) It is obtained by carrying out 1-6 mol addition reaction of seed or propylene oxide. As these amine compounds, N, N, N'-trimethyl-N'-hydroxyethyl propanediamine, N, N, N'-trimethyl-N'-hydroxyethyl neopentanediamine, N, N, N ' -Trimethyl-N'-hydroxyethylhexanediamine, N, N, N'-trimethyl-N'-hydroxyethylhexadecyldiamine, N, N, N'-triethyl-N'-hydroxyethylpropanediamine, 4- (N-hydroxyethyl-N-methylamino) -1-diethylaminopentane, N, N, N'-triethyl-N'-hydroxyethylhexanediamine, N-((N, N-hydroxy Hydroxyethylmethyl) aminoethyl) piperidine, N-((N, N-hydroxyethylmethyl) aminoethyl) -N'-methylpiperazine, N-((N, N-hydroxyethylmethyl) aminopropyl Piperidine, N-((N, N-hydroxyethylmethyl) aminopropyl) -N'-methylpiperazine, N, N-bis (dimethylaminopropyl) -N'-methyl-N'-hydroxy Ethyl propanediamine, N, N-bis (diethylaminopropyl) -N'-methyl-N'-hydroxyethylpropanediamine, N, N, N'-trimethyl-N '-(2-hydroxypropyl) propane D Min, N, N, N'-trimethyl-N '-(2-hydroxypropyl) neopentanediamine, N, N, N'-trimethyl-N'-(2-hydroxypropyl) hexanediamine, N, N , N'-trimethyl-N '-(2-hydroxypropyl) hexadecyldiamine, N, N, N'-triethyl-N'-(2-hydroxypropyl) propanediamine, 4- (N- (2 -Hydroxypropyl) -N-methylamino) -1-diethylaminopentane, N, N, N'-triethyl-N '-(2-hydroxypropyl) hexanediamine, N-((N-methyl- N- (2-hydroxypropyl)) aminoethyl) piperidine, N-((N-methyl-N- (2-hydroxypropyl) -N'-methylpiperazine, N-((N-methyl- N- (2-hydroxypropyl) aminoethyl) aminopropyl) piperidine, N-((N-methyl-N- (2-hydroxypropyl) aminoethyl) aminopropyl) -N'-methylpiperazine, N, N-bis (dimethylaminopropyl) -N'-methyl-N'-methyl-N '-(2-hydroxypropyl) propanediamine, N, N-bis (diethylaminopropyl) -N'-methyl -N'-methyl-N '-(2-hydroxypropyl) propanediamine, N, N-dimethyl-N', N'-bis (hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ', N'-bis (hydroxyethyl) propanediamine, N, N-dimethyl-N', N'-bis (hydroxyethyl) neopentanediamine, N, N-dimethyl-N ', N'-bis (hydroxyethyl) hexanediamine, N, N-dimethyl-N', N'-bis (hydroxyethyl) hexadecyldiamine, N, N-diethyl-N ' , N'-bis (hydroxyethyl) ethylenediamine, N, N-diethyl-N ', N'-bis (hydroxyethyl) propanediamine, 4-bis (hydroxyethyl) amino-1-diethylaminophen Tan, N, N-diethyl-N ', N'-bis (hydroxyethyl) hexanediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N- (N, N -Bis (hydroxyethyl) aminoethyl) -N'-methylpiperazine, N- (N, N-bis (hydroxyethyl) aminopropyl) piperidine, N- (N, N-bis (hydroxyethyl ) Aminopropyl) -N'-methylpiperazine, N, N-bis (dimethylaminopropyl) -N ', N'-bis (hydroxyethyl) propanediamine, N, N-bis (diethylaminopropyl)- N ', N'-bis (hydroxyethyl) Ropandiamine, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-N', N'-bis (2-hydroxypropyl) neopentanediamine, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) hexanediamine, N, N-dimethyl-N', N'-bis (2-hydroxypropyl) hexadecyldiamine, N, N -Diethyl-N ', N'-bis (2-hydroxypropyl) ethylenediamine, N, N-diethyl-N', N'-bis (hydroxyethyl) propanediamine, 4-bis (2-hydroxy Hydroxypropyl) amino-1-diethylaminopentane, N, N-diethyl-N ', N'-bis (2-hydroxypropyl) hexanediamine, N- (N, N-bis (2-hydroxypropyl Aminoethyl) piperidine, N- (N, N-bis (2-hydroxypropyl) aminoethyl) -N'-methylpiperazine, N- (N, N-bis (2-hydroxypropyl) amino Propyl) piperidine, N- (N, N-bis (2-hydroxypropyl) aminopropyl) -N'-methylpiperazine, N, N-bis (dimethylaminopropyl) -N ', N'-bis (2-hydroxypropyl) propanediamine, and N, N-bis (die Aminopropyl) -N ', N'- bis (2-hydroxypropyl) propane-diamine. Among them, N, N, N'-trimethyl-N'-hydroxyethylpropanediamine, N, N, N'-trimethyl-N'-hydroxyethyl neopentanediamine, N, N, N'-trimethyl-N '-Hydroxyethylhexanediamine, N, N-dimethyl-N', N'-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl Neopentanediamine, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) hexanediamine, N, N-dimethyl-N', N'-bis (hydroxyethyl) propanediamine, N , N-dimethyl-N ', N'-bis (hydroxyethyl) neopentanediamine, N, N-dimethyl-N', N'-bis (hydroxyethyl) hexanediamine, N- (N, N-bis (Hydroxyethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N'N'-bis (hydroxyethyl) propanediamine, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) ethylenediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N ', N'-bis (hydroxy Oxyethyl) ethylenediamine, and N, N- Bis (dimethylaminopropyl) -N ', N'-bis (hydroxyethyl) propanediamine is more preferred due to their high catalytic reactivity. Moreover, the compound represented by the said General formula (3), and R <11>, such as N, N, N'-trimethyl-N'-hydroxyethylethylenediamine, represent a substituent of 2 or less carbon atoms may use the polyol of this invention. You cannot form a foam. In addition, it is a reactive catalyst and has a strong migration from the foam, and has a bad smell. Therefore, these compounds cannot be said to be excellent catalysts in the process according to the invention.
[162] In the method according to the present invention, examples of the amine compound represented by the general formula (4) include N, N-dimethyl-1-propanolamine, N, N-dimethyl-1-butanolamine, N, N-dimethyl- 1-pentanolamine, N, N-dimethyl-1-hexanolamine, N, N-dimethyl-1-hexadecanolamine, N, N-diethyl-1-propanolamine, N, N-diethyl- 1-butanolamine, N, N-diethyl-1-pentanolamine, N, N-diethyl-1-hexanolamine, N, N-diethyl-1-hexadecanolamine, N, N-di Propyl-1-propanolamine, N, N-dipropyl-1-hexanolamine, N, N-dipropyl-1-hexadecanolamine, 1-propanolaziridine, 1-hexanoaziridine, 1-hexa Decanolaziridine, 1-propanolpyrrolidine, 1-hexanolpyrrolidine, 1-hexadecanolpyrrolidine, 1-propanol-N-methylpiperazine, 1-hexanol-N-methylpiperazine, 1-hexa Decanol-N-methylpiperazine, 1-propanol morpholine, 1-hexanol phospholine, 1-hexadecanol morpholine, 5-dimethylamino-3-methyl-1-pentanol, and 5-diethyla It comprises a no-3-methyl-1-pentanol. Among them, N, N-dimethyl-1-hexanamine, N, N-dimethyl-1-propanolamine, 1-hexanolpyrrolidine, 1-hexanolpiperidine, and 1-hexanolmorpholine are high in their More preferred due to catalysis. Moreover, the compound represented by the said General formula (4) and R16, such as N, N- dimethylethanolamine, which shows a substituent of 2 or less carbon atoms cannot form a favorable foam even if using the polyol of this invention. In addition, it is a reactive catalyst and has a strong migration from the foam, and has a bad smell. Therefore, these compounds cannot be said to be excellent catalysts in the process according to the invention.
[163] In the method according to the present invention, examples of the amine compound represented by the formula (5) include N- (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxybutyl) -N, N', N ", N" -tetra Methyldiethylenetriamine, N- (2-hydroxypentyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxyhexyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxyethyl) -N, N ', N ", N"', N "'-pentamethyltriethylenetetraamine, N- (2- Hydroxyethyl) -N, N ', N ", N"', N "'-pentamethyltriethylenetetraamine, N- (2-hydroxypropyl) -N, N', N", N "', N "'-pentamethyltriethylenetetraamine, N- (2-hydroxybutyl) -N, N', N", N "', N"'-pentamethyltriethylenetetraamine, N- (2-hydroxy Oxypentyl) -N, N ', N ", N"', N "'-pentamethyltriethylenetetraamine, N- (2-hydroxyhexyl) -N, N', N", N "', N "'-Pentamethyltriethylenete Triamine, N- (2-hydroxyethyl) -N, N ', N ", N"', N "", N ""-hexamethyltetraethylenepentaamine, N- (2-hydroxypropyl)- N, N ', N ", N"', N "", N ""-hexamethyltetraethylenepentaamine, N- (2-hydroxybutyl) -N, N ', N ", N"', N "", N ""-hexamethyltetraethylenepentaamine, N- (2-hydroxypentyl) -N, N ', N ", N"', N "", N ""-hexamethyltetraethylenepentaamine And N- (2-hydroxyhexyl) -N, N ', N ", N"', N "", N ""-hexamethyltetraethylenepentaamine. Among them, N- (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, and N- (2-hydroxypropyl) -N, N', N ", N "-tetramethyldiethylenetriamine is more preferred due to their high catalytic reactivity.
[164] In the method according to the invention, examples of the amine compound represented by the formula (6) include 2-((2- (2- (dimethylamino) ethoxy) ethyl) methylamino) ethanol, 1-((2- (2- (dimethylamino) ethoxy) ethyl) methylamino) -2-propanol, 2-((2- (2- (2- (dimethylamino) ethoxy) ethoxy) ethyl) methylamino) ethanol and 1 -((2- (2- (2- (dimethylamino) ethoxy) ethoxyethyl) methylamino) -2-propanol. Among them, 2-((2- (2- (dimethylamino)) Methoxy) ethyl) methylamino) ethanol and 1-((2- (2- (dimethylamino) ethoxy) ethyl) methylamino) -2-propanol are more preferable from the viewpoint of catalytic activity.
[165] The amine compounds represented by the formulas (1) to (6) can be easily prepared by conventional methods.
[166] The compound represented by the above formula (1) is obtained by, for example, reacting the corresponding imidazole with acrylonitrile, followed by amination by hydrolysis, reaction with propylene oxide or ethylene oxide, or the like.
[167] In the case of the compound represented by the formula (2), for example, N, N-dimethylpropanediamine, N, N-diethylpropanediamine and the like are dialkylaminoprop obtained from the reaction of dimethylamine, diethylamine and acrylonitrile. Obtained from the hydrolysis of pionitrile. The bis (dimethylaminepropyl) propanediamine is obtained by hydrolyzing a reaction product of bis (dimethylaminopropyl) amine and acrylonitrile, which are by-products of the dialkylaminopropionitrile reaction.
[168] The compound represented by the formula (3) is obtained by addition reaction of ethylene oxide and propylene oxide to the amine compound of formula (2) as described above.
[169] The compound represented by the formula (4) is obtained by reacting a corresponding diol with dimethylamine and the like.
[170] The compound represented by the formula (5) and the compound represented by the formula (6) are obtained by reacting the corresponding amines with alkylene oxides.
[171] If necessary, the catalyst used in the process according to the invention may be used after dilution with a solvent. The solvent is not particularly limited as long as it is usually used. Examples of the solvent include dipropylene glycol, ethylene glycol, 1,4-butanediol, diethylene glycol, and water.
[172] The usage-amount of these catalysts is 0.01-5 weight part normally per 100 weight part, Preferably it is 0.05-3 weight part. If the amount of the catalyst used is too high, the productivity of the polyurethane resin is improved, but the amount of volatile amine is also increased, which is not preferable. The catalyst composition of the present invention reacts with a polyisocyanate, which is a polyurethane water support, and is immobilized in a polyurethane resin skeleton. The immobilized catalyst of the present invention does not decompose even when exposed to high temperatures. Therefore, the catalyst composition of this invention does not exist as a free amine in a polyurethane resin, and a volatile amine does not come out. That is, in the polyurethane resin product using the catalyst composition of the present invention, it is possible to prevent the aforementioned various problems such as odor and fogging caused by volatile amines. Moreover, when the catalyst of this invention is used for manufacture of a polyurethane resin, in polyurethane products etc., it shows the outstanding moldability, such as the improvement of the cell drying spot on a foam surface, hardening of resin also improves productivity.
[173] The catalyst used in the method for producing a polyurethane according to the present invention is the catalyst of the present invention described above, but other catalysts may also be used in combination within the scope not departing from the functions of the present invention. Other catalysts include conventional catalysts such as tertiary amines and quaternary ammonium salts.
[174] Examples of tertiary amines include N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N ", N"- Pentamethyldiethylenetriamine, N, N, N ', N ", N" -pentamethyl- (3-aminopropyl) ethyldiamine, N, N, N', N ", N" -pentamethyldipropylenetri Amine, N, N, N ', N'-tetramethylganidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-s-triazine, 1,8-diazabicyclo [ 5.4.0] undecene-7, triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N ' Dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1- Isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole.
[175] Quaternary ammonium salts that may be used include tetraalkylammonium halides (eg tetraalkylammonium chloride), tetraalkylammonium hydroxides (eg tetraalkylammonium hydroxide), tetraalkylammonium organic acid salts (eg tetraalkylammonium 2-ethylhexane Acid salts, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate).
[176] The process according to the invention is characterized in that no tin-based catalyst is used. In particular, as mentioned in the present invention, the tin-based catalysts may be selected from the following examples: tinner's diacetate, stanus dioctoate, stanner's dioleate, stanner's dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyl Conventional organic tin compounds such as tin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate.
[177] The process according to the invention comprises at least 5% by weight or more of oxyethylene groups (relative to the weight of the total polyol) inside the polyol chain, having a terminal secondary OH group (A) and a terminal (total polyol) At least 5% by weight of the polyether polyol (B), which is a primary OH group, is used in combination.
[178] As the polyether polyol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol are used as the initiator, and ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter, By addition polymerization of alkylene oxides represented by PO, for example by the method described in Gunter Oertel "Polyuretnane Handbook (1985), pages 42-53, published by Hanser Publishers (Germany). Examples of the addition polymerization reaction of PO and EO include (a) addition polymerization of EO after addition polymerization of PO, further block copolymerization reaction of addition polymerization of PO and EO, and (b) PO and Copolymerization reaction of addition polymerization of PO is further included after the random reaction which copolymerizes EO randomly, Any of these methods can be used.
[179] When addition polymerization of an epoxide compound, it is also possible to use a basic catalyst. As an example of the timing of the catalyst input,
[180] (a) the method of adding a catalyst simultaneously with the polyhydric alcohol which is an initiator, and performing addition polymerization of an epoxide compound; And
[181] and (b) a method in which a catalyst is added after the polyhydric alcohols as the initiator and the epoxide compound are reacted without a catalyst, and the addition polymerization of the epoxide compound is further performed.
[182] In the method according to the invention, any of these can be used. Examples of basic catalysts include alkali metal compounds, alkaline earth metal compounds, amine compounds.
[183] Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide; And carbonates of alkali metals or alkaline earth metals such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. Moreover, hydrogencarbonate, such as potassium hydrogencarbonate and sodium hydrogencarbonate, can also be used. Examples of the amine compound include triethylamine, dimethylethanolamine, pyridine, methyldimethylamine, tri-n-propylamine, dimethylpalmitylamine, dimethyloctylamine, phenoxyimine and the like. In addition, recently,
[184]
[185] (Wherein M represents Zn, Fe, Co, Ni, Al, Sr, Mn, Cr, Cu, Sn, etc .; M 'represents Fe, Co, Cr, Mn, Ni, V, etc .; R is Organic ligands, ethers, ketones, aldehydes, esters, alcohols, amides, and the like, a , b , x and y each represent a natural number which is changed by the valence and coordination number of the metal, and c and d are changed by the coordination number. Indicates a positive number.)
[186] A composite metal cyanide compound catalyst represented by the above formula, and a phosphase such as tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxy and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium methoxide Ium can be used as a catalyst. These catalysts can also be used individually or in combination of 2 or more types.
[187] Usually, as mentioned above, after preparing a polyol, the basic catalyst used by post-processing is removed. Examples of post-processing methods are
[188] (a) neutralization treatment with at least one neutralizing agent selected from inorganic acids (such as hydrochloric acid, phosphoric acid, lactic acid), organic acids (such as formic acid, acetic acid, oxalic acid, succinic acid, phthalic acid, maleic acid) and carbon dioxide;
[189] (b) a method of treating with an ion exchange resin; And
[190] (c) a method of treating with an adsorbent.
[191] The polyol may also be purified using water, a solvent inert to the polyol, or a mixture of water and a solvent.
[192] Among these polyols, polyether polyols prepared by using glycerine or trimethiololpropane as an initiator and adding EO and PO are particularly preferred. However, in the polyether polyol (A), the addition position of EO and PO may be random in the polyol chain, the addition to the terminal may allow only PO, and the addition ratio of EO and PO is 5% by weight of EO. That's it. Moreover, the molecular weight of a polyether polyol (B) is the range of 1,500-7,000 normally, Preferably it is the range of 2,000-5,000. When this is represented by the hydroxyl value, a hydroxyl value is normally the range of 24-112 mgKOH / g, Preferably it is the range of 33-84 mgKOH / g.
[193] In the process according to the invention, the choice of polyols is important. For example, in the case of using a general-purpose polyol obtained by adding only PO to glycerin, problems such as deforming and significantly impaired breathability occur. Moreover, even if the catalyst of the present invention is used, the air permeability of the foam is deteriorated, and a good foam cannot be formed.
[194] When using only the polyether polyol (A) of this invention as a polyol independently, it is difficult to form a low density foam. In addition, when a conventional amine catalyst is used, there is a problem that deforming occurs, cracks are generated in the foam, or the surface of the foam is broken and peeled off, so that a good foam cannot be formed.
[195] Moreover, when only the polyether polyol (B) of this invention is used alone as a polyol, there exists a problem that the ratio of independent bubbles in a foam increases. As a result, the breathability of the foam may be significantly deteriorated and shrinkage of the foam may occur. Moreover, even if the catalyst of the present invention is used, it is difficult to improve breathability, and thus a good foam cannot be formed.
[196] As a polyol, even if the polyether polyol (A) of this invention and general purpose polyol obtained by adding only PO to glycerin are combined, serious problems, such as deforming and breathability deteriorate significantly, arise. Moreover, even if the catalyst of the present invention is used, the air permeability of the foam is deteriorated, and a good foam cannot be formed. Similarly, even if the polyether polyol (B) of the present invention is used in combination with a general-purpose polyol obtained by adding only PO to glycerin, serious problems such as deforming and poor air permeability are caused. In addition, even if the catalyst of the present invention is used, the air permeability of the foam is deteriorated, and a good foam cannot be formed. That is, by using the polyether polyol (A) and polyether polyol (B) of the present invention in combination, and using the catalyst of the present invention, it is possible to form a good foam without using a tin catalyst.
[197] Although the use ratio of the polyether polyol (A) and the polyether polyol (B) of the present invention is not limited, it is 10/90 to 90/10 in weight percent ratio, preferably 20/80 to 80/20, more preferably It is 30/70 ~ 70/30. If the use ratio of the polyether polyol (A) is too high, cracks are likely to occur, and the foam density is increased. On the contrary, when the use ratio of the polyether polyol (B) is too high, the air permeability of the foam is deteriorated.
[198] In addition, even when the polyether polyol (A) and the polyether polyol (B) of the present invention are used in combination, when an amine catalyst other than the catalyst of the present invention is used, deforming occurs, cracks are generated in the foam, There is a problem that the foam surface is broken and peeled off, and a good foam cannot be formed.
[199] The polyisocyanate used in the present invention is toluene diisocyanate (hereinafter referred to as TDI) and / or a derivative thereof. Examples of TDI include 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and mixtures thereof. Derivatives of TDI are, for example, terminal isocyanate prepolymer derivatives. In the manufacture of the flexible foam of the present invention, a mixture of 2,4-toluene diisocyanate and 2,6-toluene isocyanate which can be easily obtained industrially can be preferably used.
[200] In the process according to the invention, the isocyanate index (isocyanate group / active hydrogen group which can react with this isocyanate group) is not particularly limited, but is generally in the range of 60 to 130.
[201] In the method according to the present invention, auxiliary agents such as foaming agents, foam stabilizers, crosslinking agents or chain extenders, colorants, flame retardants, and antioxidants can be used as necessary.
[202] As the blowing agent used in the present invention, water and / or carbon dioxide is preferable. It is also possible to use a halogenated hydrocarbon as a blowing agent. Examples of halogenated hydrocarbons include conventional halogenated methanes such as methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichlorotrifluoromethane, dichloromonofluoromethane, halogenated ethane. Foaming agents are particularly preferred water. The amount of water used may vary depending on the density of the intended foam, but is usually 0.5 parts by weight or more per 100 parts by weight of polyol, preferably 0.5 to 8 parts by weight, and more preferably 2 to 5.5 parts by weight. If the amount of water is less than 0.5 parts by weight, the foaming ratio is extremely low, and a low density foam cannot be formed. On the contrary, when the amount of water is 8 parts by weight or more, foaming becomes unstable and deforming is likely to occur, thereby causing problems such as the inability to form a foam or the occurrence of scorch.
[203] In the process according to the invention, foam stabilizers can be used if necessary. This foam stabilizer can use conventional organic silicone surfactants in the present invention. The amount of foam stabilizer to be used is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of polyol.
[204] In the process according to the invention, crosslinking agents or chain extenders can be used if necessary. Examples of crosslinking agents or chain extenders include low molecular weight polyhydric alcohols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and glycerin; And polyamines such as ethylenediamine, xylenediamine and methylene bis-o-chloroaniline. Among these, diethanolamine and triethanolamine are preferable.
[205] In the method according to the present invention, colorants, flame retardants, antioxidants, other conventional additives, and the like may also be used, if necessary. Examples of the flame retardant include, but are not limited to, chloroalkyl phosphate, dimethylmethyl phosphate, polymeric phosphate, bromine-phosphate, organic bromine compound, ammonium polyphosphate, diethyl phosphate, bishydroxyethyl phosphate, aminoethyl phosphate, Neopentylpromide adipate, dibromopropanol, dibromoneopentyl glycol, brominated polyethers, and the like. The kind and addition amount of these additives can fully be used in the range normally used, without deviating from a normal form and procedure.
[206] EMBODIMENT OF THE INVENTION Hereinafter, although 1st Embodiment of this invention is described with reference to an Example and a comparative example, this invention is not limited only to these Examples.
[207] Formulation Example 1
[208] 184.0 g of glycerin (reagent) and 4 g of potassium hydroxide (reagent) were placed in a 10 liter autoclave equipped with a thermometer and a stirrer and heated to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide (1,890.2 g) was introduced for 4 hours using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature. Next, using a metering pump, 2,035.6 g of ethylene oxide was introduced for 5 hours. The reaction was continued for an additional 3 hours while maintaining the reaction temperature. Next, 1,890.2 g of propylene oxide was introduced for 4 hours using a metering pump, and the reaction was continued for 2 hours while maintaining the reaction temperature. After the end of the polymerization, the reaction mixture was purified by neutralization, dehydration, and filtration.
[209] The obtained polyol was hydroxyl value 56 mg-KOH / g, viscosity 485 cPs / 25 degreeC, and ethylene oxide content was 35 weight%. The obtained polyol was referred to as "polyol A" and was used in the following examples and comparative examples.
[210] Formulation Example 2
[211] 184.0 g of glycerin (reagent) and 4 g of potassium hydroxide (reagent) were placed in a 10 liter autoclave equipped with a thermometer and a stirrer and heated to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide (4,652.8 g) was introduced for 8 hours using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature. Next, using a metering pump, 1,163.2 g of ethylene oxide was introduced for 3 hours. The reaction was continued for an additional 3 hours while maintaining the reaction temperature. After the end of the polymerization, the reaction mixture was purified by neutralization, dehydration, and filtration. The obtained polyol was hydroxyl value 56 mg-KOH / g, viscosity 495 cPs / 25 degreeC, and ethylene oxide content was 20 weight%. The obtained polyol was referred to as "polyol C" and was used in the following examples and comparative examples.
[212] Examples 1-5, Comparative Examples 1-13
[213] By changing the catalyst and the polyol, by mixing the polyol and polyisocyanate (isocyanate index = 105) shown in Tables 1 to 3, the foaming agent and the foam stabilizer were adjusted as shown in Table 1 to adjust the flexible polyurethane foam. The reactivity (cream time and rise time) of the flexible polyurethane foam and the physical properties (density and breathability) of the foam molding were measured and evaluated. The evaluation result was shown to Tables 1-3.
[214] Foam condition
[215] Temperature of raw material liquid: 25 ± 1 ℃
[216] Stirring Speed: 3,000 rpm (for 5 seconds)
[217] Mold: Aluminum box (Size: 25 × 25 × 25 cm)
[218] Mold temperature: 45 ℃
[219] Curing was performed under heating for 1 hour while maintaining at 45 ° C. after foaming.
[220] Metric
[221] The following items were measured.
[222] Reactivity:
[223] Cream time: start time of forming (seconds)
[224] Rise time: Number of seconds to reach maximum foam height
[225] Density of foam:
[226] Measure the density of the test piece having a size of 20 × 20 × 20 cm from the center of the foam (kg / m ³ )
[227] Breathable Foam:
[228] Dow Air Flow Apparatus was used.
[229] Evaluation of formability:
[230] The size of the cracks inside the foam was observed and ranked according to the following five grades.
[231] 1: almost none
[232] 2: small
[233] 3: medium
[234] 4: large
[235] 5: very large
[236] Evaluation of Surface Brittleness:
[237] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[238] 1: not peeled off at all
[239] 2: slightly peeled off
[240] 3: medium
[241] 4: much peeling off
[242] 5: Peeling from surface to depth of 1 cm or more.
[243] Example 1Example 2Example 3Example 4Example 5Comparative Example 1 Formula (part by weight) Polyol A ¹⁾ 100100100100100Polyol B ²⁾ 100 Isocyanate ³⁾ 59.959.959.959.959.959.9 DMIZ ⁴⁾ 0.70.7 NMIZ ⁵⁾ 0.75 IBIZ ⁶⁾ 0.8 2H1MIZ ⁷⁾0.8 APIZ ⁸⁾ 0.9water5.05.05.05.05.05.0 Foam stabilizer ⁹⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time9999910 Rise time111108105100102113 Foam Properties Core density (㎏ / m ³ )25.125.525.425.325.928.5 Formability ¹⁰⁾ OneOneOneOneOne2 Surface brittleness ¹¹⁾ OneOneOneOneOneOne Breathable (ft ³ / min)3.53.02.83.43.10.4
[244] week:
[245] 1) Polyether polyol A: A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with ethylene oxide, followed by propylene oxide. Ethylene oxide ratio = 35%, terminal propylene oxide ratio = 100%
[246] 2) Polyether polyol B: Polyether polyol (GP3000 by Sanyo Chemical Co., Ltd.) of hydroxyl value 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin.
[247] 3) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[248] 4) 70 wt% ethylene glycol solution of 1,2-dimethylimidazole (TOYOCAT-DM70 manufactured by Tosoh Corporation)
[249] 5) 1-methylimidazole (reagent)
[250] 6) 1-isobutyl-2-methylimidazole (manufactured by Katsuzai Chemical Co., Ltd.)
[251] 7) 1-hydroxypropyl-2-methylimidazole (synthetic product)
[252] 8) 1-aminopropyl-2-methylimidazole (synthetic product)
[253] 9) Silicone foam stabilizer made by Japan Unicar
[254] 10) Evaluation of moldability:
[255] The size of cracks in the foam was observed and classified into the following five steps.
[256] 1: almost none
[257] 2: small
[258] 3: medium
[259] 4: large
[260] 5: very large
[261] 11) Evaluation of surface brittleness:
[262] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[263] 1: not peeled off at all
[264] 2: slightly peeled off
[265] 3: medium
[266] 4: much peeling off
[267] 5: Peeling from surface to depth of 1 cm or more.
[268] Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7 Formula (part by weight) Polyol A ¹⁾ 100100100 Polyol B ²⁾ 100Polyol C ³⁾ 100 Isocyanate ⁴⁾ 59.928.491.459.959.959.9 DMIZ ⁵⁾ 0.70.70.7 0.7 TEDA-L33 ⁶⁾0.550.550.55 water5.01.98.15.05.05.0 Foam stabilizer ⁷⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time8913151812 Rise time10010289108115105 Foam Properties Core density (㎏ / m ³ )22.833.5Deforming24.229.2Shrink Formability ⁸⁾ One2-34- Surface brittleness ⁹⁾ OneOne-35- Breathable (ft ³ / min)<0.10.5-2.01.0-
[269] week:
[270] 1) Polyether polyol A: A polyether polyol having a hydroxyl value of 56 mg-KOH / g, synthesized by reacting glycerine with ethylene oxide, followed by propylene oxide. Ethylene oxide ratio = 35%, terminal Propylene oxide ratio = 100%
[271] 2) Polyether polyol B: Polyether polyol (GP3000 by Sanyo Chemical Co., Ltd.) of hydroxyl value 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin.
[272] 3) Polyether polyol C: A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal propylene oxide ratio = 60%
[273] 4) T-80: Japanese toluene diisocyanate
[274] 5) 70 wt% ethylene glycol solution of 1,2-dimethylimidazole (TOYOCAT-DM70 manufactured by Tosoh Corporation)
[275] 6) 33.3 wt% dipropylene glycol solution of triethylenediamine (TEDA-L33 from Tosoh Corporation)
[276] 7) Silicone foam stabilizer made by Nippon Unicar Company
[277] 8) Evaluation of moldability:
[278] The size of cracks in the foam was observed and classified into the following five steps.
[279] 1: almost none
[280] 2: small
[281] 3: medium
[282] 4: large
[283] 5: very large
[284] 9) Evaluation of Surface Brittleness:
[285] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[286] 1: not peeled off at all
[287] 2: slightly peeled off
[288] 3: medium
[289] 4: much peeling off
[290] 5: Peeling from surface to depth of 1 cm or more.
[291] Comparative Example 8Comparative Example 9Comparative Example 10Comparative Example 11Comparative Example 12Comparative Example 13 Formula (part by weight) Polyol A ¹⁾ 100100100100100100 Isocyanate ²⁾ 59.959.959.959.959.959.9 MR ³⁾ 0.4NP ⁴⁾ 0.4 DMEA ⁵⁾ 1.0 DBU ⁶⁾0.56 TRC ⁷⁾ 1.1K15 ⁸⁾ 1.1 water5.05.05.05.05.05.0 Foam stabilizer ⁹⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time13139151111 Rise time10110998110148108 Foam Properties Core density (㎏ / m ³ )24.926.329.224.324.324.5 Formability ¹⁰⁾ 33422One Surface brittleness ¹¹⁾ 555553 Breathable (ft ³ / min)1.61.81.00.81.51.3
[292] week:
[293] 1) Polyether polyol A: A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with ethylene oxide, followed by propylene oxide. Ethylene oxide ratio = 35%, terminal propylene oxide ratio = 100%
[294] 2) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[295] 3) tetramethylhexamethylenediamine (TOYOCAT-MR manufactured by Tosoh Corporation)
[296] 4) 1- (dimethylamino) -4-methylpiperazine (TOYOCAT-NP manufactured by Tosoh Corporation)
[297] 5) N, N-dimethylaminoethanol (reagent)
[298] 6) 1,8-diazabicyclo [5.4.0] undecene-7 (reagent)
[299] 7) 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine (reagent)
[300] 8) 15 wt% diethylene glycol solution of potassium 2-ethylhexanoate (reagent)
[301] 9) Silicone foam stabilizer made by Japan Unicar
[302] 10) Evaluation of moldability:
[303] The size of cracks in the foam was observed and classified into the following five steps.
[304] 1: almost none
[305] 2: small
[306] 3: medium
[307] 4: large
[308] 5: very large
[309] 11) Evaluation of surface brittleness:
[310] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[311] 1: not peeled off at all
[312] 2: slightly peeled off
[313] 3: medium
[314] 4: much peeling off
[315] 5: Peeling from surface to depth of 1 cm or more.
[316] As apparent from Tables 1 to 3, according to the examples of the present invention, it is found that the moldability is good, the surface brittleness is not found, and a urethane foam having high air permeability is obtained.
[317] On the contrary, as shown in Comparative Examples 1 and 2, even when the catalyst of the present invention is used, when the polyol of the present invention is not used, a urethane foam having poor breathability and a high density is obtained, which is not suitable for the market demand. It can be seen that.
[318] As shown in Comparative Examples 3 and 4, when the amount of water is 2 pbw or less, an extremely dense foam is formed, or when the amount of water is extremely high, the formation of the foam is unstable, which may result in deforming. That is, it is important that the amount of water is used in an amount of 2 to 8 parts by weight per 100 parts by weight of polyol.
[319] As shown in Comparative Examples 5 and 6, when a catalyst other than the catalyst of the present invention is used, excellent urethane foam cannot be obtained by using only polyol A or B.
[320] Further, as is apparent from Comparative Example 7, when polyol C is used, a problem of shrinkage of shrinkage occurs.
[321] In addition, as can be seen from Comparative Examples 8 to 13, when a catalyst other than the catalyst of the present invention is used, a urethane foam having poor moldability and a very brittle surface is obtained, which is not suitable for market demand. not.
[322] EMBODIMENT OF THE INVENTION Hereinafter, although 2nd Embodiment of this invention is described with reference to a following example and a comparative example, this invention is not limited only to these Examples.
[323] Formulation Example 3
[324] Preparation of polyether polyol (A)
[325] 184.0 g of glycerin (reagent) and 4 g of potassium hydroxide (reagent) were placed in a 10 liter autoclave equipped with a thermometer and a stirrer and heated to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide (2,442.7 g) was introduced for 4 hours using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature. Next, using a metering pump, 930.6 g of ethylene oxide was introduced for 5 hours. The reaction was continued for an additional 3 hours while maintaining the reaction temperature. Next, 2,442.7 g of propylene oxide was introduced for 4 hours using a metering pump, and the reaction was continued for 2 hours while maintaining the reaction temperature. After the end of the polymerization, the reaction mixture was purified by neutralization, dehydration, and filtration. The obtained polyol was hydroxyl value 56 mg-KOH / g, viscosity 485 cPs / 25 degreeC, and ethylene oxide content was 16 weight%. NMR analysis showed no primary OH groups at the polyol chain ends, but secondary OH groups were found in all of them. Therefore, the obtained polyol was referred to as "polyol (A)" and used in the following examples and comparative examples.
[326] Formulation Example 4
[327] Preparation of polyether polyol (B)
[328] 184.0 g of glycerin (reagent) and 4 g of potassium hydroxide (reagent) were placed in a 10 liter autoclave equipped with a thermometer and a stirrer and heated to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide (4,303.8 g) was introduced for 8 hours using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature. Next, using a metering pump, 1,512.2 g of ethylene oxide was introduced for 3 hours. The reaction was continued for an additional 3 hours while maintaining the reaction temperature. After the end of the polymerization, the reaction mixture was purified by neutralization, dehydration, and filtration. The obtained polyol was hydroxyl value 56 mg-KOH / g, and viscosity 495 cPs / 25 degreeC. NMR analysis showed that the proportion of primary OH groups at the ends of the polyol chains was 72.5 mol%. Therefore, the obtained polyol was referred to as "polyol (B) and used in the following examples and comparative examples.
[329] Examples 6-14, Comparative Examples 14-26
[330] The catalyst and the polyol were changed, and by mixing the polyol and polyisocyanate shown in Tables 4 to 7 (isocyanate index = 105), the foaming agent and the foam stabilizer were adjusted as shown in Table 4 to adjust the flexible polyurethane foam. The reactivity (cream time and rise time) of the flexible polyurethane foam and the physical properties (density and breathability) of the foam molding were measured and evaluated. The evaluation result was shown to Tables 4-7.
[331] Foam condition
[332] Temperature of raw material liquid: 25 ± 1 ℃
[333] Stirring Speed: 3,000 rpm (for 5 seconds)
[334] Mold: Aluminum box (Size: 25 × 25 × 25 cm)
[335] Mold temperature: 45 ℃
[336] Curing was performed under heating for 1 hour while maintaining at 45 ° C. after foaming.
[337] Metric
[338] The following items were measured.
[339] Reactivity:
[340] Cream time: start time of forming (seconds)
[341] Rise time: Number of seconds to reach maximum foam height
[342] Density of foam:
[343] Measure the density of the test piece having a size of 20 × 20 × 20 cm from the center of the foam (kg / m ³ )
[344] Breathable Foam:
[345] Dow Air Flow Apparatus was used.
[346] Evaluation of formability:
[347] The size of the cracks inside the foam was observed and ranked according to the following five grades.
[348] 1: almost none
[349] 2: small
[350] 3: medium
[351] 4: large
[352] 5: very large
[353] Evaluation of Surface Brittleness:
[354] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[355] 1: not peeled off at all
[356] 2: slightly peeled off
[357] 3: medium
[358] 4: much peeling off
[359] 5: Peeling from surface to depth of 1 cm or more.
[360] Example 6Example 7Example 8Example 9Example 10Comparative Example 11 Formula (part by weight) Polyol (A) ¹⁾ 404040404040 Polyol (B) ²⁾ 606060606060 Isocyanate ³⁾ 59.959.959.959.959.959.9 DMIZ ⁴⁾ 0.45NMIZ ⁵⁾ 0.45 IBIZ ⁶⁾ 0.5 TEDA-L33 ⁷⁾0.4 TEDA-L33 / ET ⁸⁾ 0.32 / 0.04TEDA-L33 / ET ⁹⁾ 0.32 / 0.04 water5.05.05.05.05.05.0 Foam stabilizer ¹⁰⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time888111010 Rise time116110109100102105 Foam Properties Core density (㎏ / m ³ )22.522.923.022.121.521.9 Formability ¹⁰⁾ OneOneOneOneOne2 Surface brittleness ¹¹⁾ OneOneOneOneOneOne Breathable (ft ³ / min)3.02.82.51.01.21.2
[361] week:
[362] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[363] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[364] 3) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[365] 4) 70 wt% ethylene glycol solution of 1,2-dimethylimidazole (TOYOCAT-DM70 manufactured by Tosoh Corporation)
[366] 5) 1-methylimidazole (reagent)
[367] 6) 1-isobutyl-2-methylimidazole (manufactured by Katsuzai Chemical Co., Ltd.)
[368] 7) 33.3 wt% dipropylene glycol solution of triethylenediamine (TEDA-L33 manufactured by Tosoh Corporation)
[369] 8) Bis (2-dimethylaminoethyl) ether (TOYOCAT-ET manufactured by Tosoh Corporation)
[370] 9) N, N, N ', N ", N" -pentamethyldiethylenetriamine (TOYOCAT-DT manufactured by Tosoh Corporation)
[371] 10) Silicone foam stabilizer made by Japan Unicar
[372] 11) Evaluation of moldability:
[373] The size of cracks in the foam was observed and classified into the following five steps.
[374] 1: almost none
[375] 2: small
[376] 3: medium
[377] 4: large
[378] 5: very large
[379] 12) Evaluation of surface brittleness:
[380] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[381] 1: not peeled off at all
[382] 2: slightly peeled off
[383] 3: medium
[384] 4: much peeling off
[385] 5: Peeling from surface to depth of 1 cm or more.
[386] Example 12Example 13Example 14Comparative Example 14Comparative Example 15Comparative Example 16 Formula (part by weight) Polyol (A) ¹⁾ 404040100 Polyol (B) ²⁾ 606060 100Polyol (C) ³⁾ 100 Isocyanate ⁴⁾ 59.959.959.959.959.959.9 NP ⁵⁾ 0.4NP / ET ⁶⁾ 0.32 / 0.04 NP / DT ⁷⁾ 0.32 / 0.04 DMIZ ⁸⁾0.450.450.45 water5.05.05.05.05.05.0 Foam stabilizer ⁹⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time11101011912 Rise time969092124420126 Foam Properties Core density (㎏ / m ³ )21.620.820.925.322.828.7 Formability ¹⁰⁾ OneOneOneOneOne2 Surface brittleness ¹¹⁾ OneOneOneOneOneOne Breathable (ft ³ / min)1.21.51.43.1≤0.10.4
[387] week:
[388] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[389] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[390] 3) Polyether polyol (C): A polyether polyol having a hydroxyl value of 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin. (GP3000 made by Sanyo Hwaseong company)
[391] 4) T-80: Japanese toluene diisocyanate
[392] 5) 1- (dimethylamino) -4-methylpiperazine (TOYOCAT-NP manufactured by Tosoh Corporation)
[393] 6) Bis (2-dimethylaminoethyl) ether (TOYOCAT-ET manufactured by Tosoh Corporation)
[394] 7) N, N, N ', N ", N" -pentamethyldiethylenetriamine (TOYOCAT-DT manufactured by Tosoh Corporation)
[395] 8) 70wt% ethylene glycol solution of 1,2-dimethylimidazole (TOYOCAT-DM70 by Tosoh Corporation)
[396] 9) Silicone foam stabilizer made by Japan Unicar
[397] 10) Evaluation of moldability:
[398] The size of cracks in the foam was observed and classified into the following five steps.
[399] 1: almost none
[400] 2: small
[401] 3: medium
[402] 4: large
[403] 5: very large
[404] 11) Evaluation of surface brittleness:
[405] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[406] 1: not peeled off at all
[407] 2: slightly peeled off
[408] 3: medium
[409] 4: much peeling off
[410] 5: Peeling from surface to depth of 1 cm or more.
[411] Comparative Example 17Comparative Example 18Comparative Example 19Comparative Example 20Comparative Example 21Comparative Example 22 Formula (part by weight) Polyol (A) ¹⁾ 100 404040 Polyol (B) ²⁾ 100 606060 Polyol (C) ³⁾ 100 100 Isocyanate ⁴⁾ 59.959.959.959.959.959.9 TEDA-L33 ^{5) /} ET ⁶⁾ 0.32 / 0.040.32 / 0.040.32 / 0.04 DMEA ⁷⁾0.6 TRC ⁸⁾ 0.6DBO ⁹⁾ 1.0 water5.05.05.05.05.05.0 Foam stabilizer ¹⁰⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time11912101211 Rise time108100108105108111 Foam Properties Core density (㎏ / m ³ )22.921.323.521.4ShrinkShrink Formability ¹¹⁾ 3One33-- Surface brittleness ¹²⁾ 5One52-- Breathable (ft ³ / min)1.80.10.22.1--
[412] week:
[413] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[414] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[415] 3) Polyether polyol (C): Polyether polyol (GP3000 by Sanyo Chemical Co., Ltd.) of hydroxyl value 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin.
[416] 4) T-80: Japanese toluene diisocyanate
[417] 5) 33.3 wt% dipropylene glycol solution of triethylenediamine (TEDA-L33 manufactured by Tosoh Corporation)
[418] 6) Bis (2-dimethylaminoethyl) ether (TOYOCAT-ET manufactured by Tosoh Corporation)
[419] 7) N, N-dimethylaminoethanol (reagent)
[420] 8) 1,8-diazabicyclo [5.4.0] undecene-7 (reagent)
[421] 9) 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-s-triazine (reagent)
[422] 10) Silicone foam stabilizer made by Japan Unicar
[423] 11) Evaluation of moldability:
[424] The size of cracks in the foam was observed and classified into the following five steps.
[425] 1: almost none
[426] 2: small
[427] 3: medium
[428] 4: large
[429] 5: very large
[430] 11) Evaluation of surface brittleness:
[431] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[432] 1: not peeled off at all
[433] 2: slightly peeled off
[434] 3: medium
[435] 4: much peeling off
[436] 5: Peeling from surface to depth of 1 cm or more.
[437] Comparative Example 23Comparative Example 24Comparative Example 25Comparative Example 26 Formula (part by weight) Polyol (A) ¹⁾ 40404040 Polyol (B) ²⁾ 60606060 Isocyanate ³⁾ 59.959.959.959.9 MR ⁴⁾ 0.35 NMP ⁵⁾ 1.5 NEM ⁶⁾ 2.0DB ⁷⁾1.6 water5.05.05.05.0 Foam stabilizer ⁸⁾ 1.01.01.01.0 INDEX105105105105 Responsiveness (seconds) Cream time107810 Rise time105103113112 Foam Properties Core density (㎏ / m ³ )23.524.324.623.4 Formability ¹¹⁾ 2553 Surface brittleness ¹²⁾ One552 Breathable (ft ³ / min)0.5--1.8
[438] week:
[439] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[440] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[441] 3) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[442] 4) N, N, N ', N'-tetraethylhexamethylenediamine (TOYOCAT-MR manufactured by Tosoh Corporation)
[443] 5) N-methylpiperazine (Reagent)
[444] 6) N-ethyl morpholine (reagent)
[445] 7) Dimethylbenzylamine (Reagent)
[446] 8) Silicone foam stabilizer made by Japan Unicar
[447] 9) Evaluation of formability:
[448] The size of cracks in the foam was observed and classified into the following five steps.
[449] 1: almost none
[450] 2: small
[451] 3: medium
[452] 4: large
[453] 5: very large
[454] 10) Evaluation of surface brittleness:
[455] The condition of the foam surface was observed, and the degree of peeling (surface brittleness) of the surface by hand touching was classified according to the following five grades.
[456] 1: not peeled off at all
[457] 2: slightly peeled off
[458] 3: medium
[459] 4: much peeling off
[460] 5: Peeling from surface to depth of 1 cm or more.
[461] As is apparent from Tables 4 to 7, according to the examples of the present invention, it is found that the moldability is good, the surface brittleness is not found, and a urethane foam having high air permeability is obtained. On the contrary, as shown in Comparative Examples 14 to 16, even when the catalyst of the present invention was used, when the mixed polyol of the present invention was not used, a urethane foam having poor breathability and a high density was obtained, which was suitable for the market demand. You can see that you did not. In addition, as shown in Comparative Examples 17 to 26, in the case of using a catalyst other than the catalyst of the present invention, a urethane foam having poor moldability and a considerably brittle surface is obtained, which is not suitable for market demand. Able to know.
[462] EMBODIMENT OF THE INVENTION Hereinafter, although 3rd Embodiment of this invention is described with reference to a following example and a comparative example, this invention is not limited only to these Examples.
[463] Formulation Example 5
[464] Preparation of polyether polyol (A)
[465] 184.0 g of glycerin (reagent) and 4 g of potassium hydroxide (reagent) were placed in a 10 liter autoclave equipped with a thermometer and a stirrer and heated to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide (2,442.7 g) was introduced for 4 hours using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature. Next, using a metering pump, 930.6 g of ethylene oxide was introduced for 5 hours. The reaction was continued for an additional 3 hours while maintaining the reaction temperature. Next, 2,442.7 g of propylene oxide was introduced for 4 hours using a metering pump, and the reaction was continued for 2 hours while maintaining the reaction temperature. After the end of the polymerization, the reaction mixture was purified by neutralization, dehydration, and filtration. The obtained polyol was hydroxyl value 56 mg-KOH / g, viscosity 485 cPs / 25 degreeC. NMR analysis showed no primary OH groups at the polyol chain ends, but secondary OH groups were found in all of them. Therefore, the obtained polyol was referred to as "polyol (A)" and used in the following examples and comparative examples.
[466] Formulation Example 6
[467] Preparation of polyether polyol (B)
[468] 184.0 g of glycerin (reagent) and 4 g of potassium hydroxide (reagent) were placed in a 10 liter autoclave equipped with a thermometer and a stirrer and heated to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide (4,303.8 g) was introduced for 8 hours using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature. Next, using a metering pump, 1,512.2 g of ethylene oxide was introduced for 3 hours. The reaction was continued for an additional 3 hours while maintaining the reaction temperature. After the end of the polymerization, the reaction mixture was purified by neutralization, dehydration, and filtration. The obtained polyol was hydroxyl value 56 mg-KOH / g, and viscosity 495 cPs / 25 degreeC. NMR analysis showed that the proportion of primary OH groups at the polyol chain ends was 72.5%. Therefore, the obtained polyol was referred to as "polyol (B) and used in the following examples and comparative examples.
[469] Pharmaceutics 7
[470] Preparation of 1-hydroxypropyl-2-methylimidazole
[471] 82.1 g of 2-methylimidazole (reagent) and 200 g of methanol were placed in a 1 liter autoclave equipped with a thermometer and a stirrer and subjected to nitrogen substitution, followed by heating to 100 ° C while stirring. While maintaining the temperature at 100 ° C., propylene oxide (58.1 g) was introduced for 1 hour using a metering pump and the mixture was addition polymerized at 120 ° C. under stirring. After the propylene oxide was introduced, the reaction was continued for an additional 2 hours while maintaining the reaction temperature at 120 ° C. After the completion of the reaction, the reaction mixture was distilled off to obtain 121.2 g of 1-hydroxypropyl-2-methylimidazole as the target product. Distillation conditions were 210 ° C./1.1 kPa. The obtained amine catalyst was used as "Cat-A", and it used in the following example and the comparative example.
[472] Formulation Example 8
[473] Preparation of N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) propanediamine
[474] 204.4 g of N, N-dimethylpropanediamine (reagent) was placed in a 1 liter autoclave equipped with a thermometer and a stirrer, and subjected to nitrogen substitution, followed by heating to 175 ° C while stirring. While maintaining the temperature at 175 ° C, propylene oxide (240.6 g) was introduced for 3 hours using a metering pump and the mixture was addition polymerized at 175 ° C under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature at 175 ° C. After the completion of the reaction, the reaction mixture was distilled to obtain 430.2 g of N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) propanediamine as a target product. After the pressure reduction, the low boiling material was doped with an evaporator to obtain "Cat-C", which was used in the examples and comparative examples below.
[475] Formulation Example 9
[476] Preparation of N- (2-hydroxypropyl) -N, N ', N ", N" -tetramethyldimethylenetriamine
[477] 103.2 g of dienylenetriamine (manufactured by Tosoh Corporation) was put into a 1 liter autoclave equipped with a thermometer, a thermometer, and a stirrer, and after nitrogen substitution, the mixture was heated to 80 ° C while stirring. While maintaining the temperature at 80 ° C., propylene oxide (28.1 g) was introduced for 1 hour using a metering pump and the mixture was addition polymerized at 80 ° C. under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature at 80 ° C. After the completion of the reaction, the reaction mixture was distilled to obtain 75.2 g of N- (2-hydroxypropyl) -diethylenetriamine as a target product. 75.2 g of the obtained N- (2-hydroxypropyl) -diethylenetriamine, 100 g of pure water, and R-Ni4g, which is a catalyst, were placed in a 1 liter autoclave equipped with a thermometer and a stirrer and subjected to nitrogen substitution, followed by stirring while stirring. Heated to ° C. While maintaining the temperature at 130 ° C, 151.6 g of 37% aqueous formalin aqueous solution was introduced for 2 hours using a metering pump, and the mixture was addition polymerized at 130 ° C under stirring. The reaction was continued for an additional 2 hours while maintaining the reaction temperature at 130 ° C. After the completion of the reaction, the mixture was distilled to obtain 91.2 g of N- (2-hydroxypropyl) -N, N ', N ", N" -tetramethyldimethylenetriamine as a target product. Distillation conditions were 155 ° C / 3.6 kPa. The obtained amine catalyst was referred to as "Cat-E" and used in the following examples and comparative examples.
[478] Examples 15-20, Comparative Examples 27-48
[479] By changing the catalyst and the polyol, by mixing the polyol and polyisocyanate (isocyanate index = 105) shown in Tables 8 to 12, the foaming agent and the foam stabilizer were adjusted as shown in the respective tables. The reactivity (cream time and rise time) of the flexible polyurethane foam and the physical properties (density and breathability) of the foam molding were measured and evaluated. The evaluation result was shown to Tables 8-12.
[480] In the preparation, the urethane foam was prepared under the following foaming conditions.
[481] Foam condition
[482] Temperature of raw material liquid: 25 ± 1 ℃
[483] Stirring Speed: 3,000 rpm (for 5 seconds)
[484] Mold: Aluminum box (Size: 25 × 25 × 25 cm)
[485] Mold temperature: 45 ℃
[486] Curing was performed under heating for 1 hour while maintaining at 45 ° C. after foaming.
[487] Metric
[488] The following items were measured.
[489] Reactivity:
[490] Cream time: start time of forming (seconds)
[491] Rise time: Number of seconds to reach maximum foam height
[492] Density of foam:
[493] Determination of the density of the test piece having a size of 20 × 20 × 20 cm from the center of the foam (kg / m ³ )
[494] Breathable Foam:
[495] Dow Air Flow Apparatus was used.
[496] Evaluation of formability:
[497] The size of the cracks inside the foam was observed and ranked according to the following five grades.
[498] 1: almost none
[499] 2: small
[500] 3: medium
[501] 4: large
[502] 5: very large
[503] Evaluation of Surface Brittleness:
[504] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[505] 1: not peeled off at all
[506] 2: slightly peeled off
[507] 3: medium
[508] 4: much peeling off
[509] 5: Peeling from surface to depth of 1 cm or more.
[510] Volatilization of Amine Catalyst:
[511] The amount of amine catalyst volatilized from the foam was quantified according to the method of DIN 75201-G. That is, five foams of 5x5x1 cm size were cut from the foam core density measurement and placed in a 500 ml flat bottomed flask and wrapped with aluminum foil. Next, the top cover of the detachable flask adapted to allow cooling water to flow into the air gap was covered with a 500 mL flat bottom detachable flask and fixed with a clamp. This vessel was deposited for 48 hours in an oil bath at 100 ° C. After 48 hours, methanol was flowed into the amine catalyst attached to the aluminum foil and quantified by gas chromatography. Quantitative values were expressed in amine catalyst (μg) per 1g of foam.
[512] Odor of the form:
[513] After cutting the foam core density, the foam of 5x5x5 cm size was cut into a mayonnaise bottle, covered with a lid, and ten monitors were smelled of the foam, and the odor intensity was measured.
[514] A: Almost no odor
[515] B: Slightly bad smell
[516] C: There is a bad smell
[517] D: Has strong odor
[518] Example 15Example 16Example 17Example 18Example 19Example 20 Formula (part by weight) Polyol (A) ¹⁾ 606060606060 Polyol (B) ²⁾ 404040404040 Isocyanate ³⁾ 59.959.959.959.959.959.9 Cat-A ⁴⁾ 0.8Cat-B ⁵⁾ 0.6 Cat-C ⁶⁾ 1.0 Cat-D ⁷⁾0.8 Cat-D / Cat-E ⁸⁾ 0.4 / 0.18Cat-E / Cat-F ⁹⁾ 0.4 / 0.15 water5.05.05.05.05.05.0 Foam stabilizer ¹⁰⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time999999 Rise time98105110107103105 Foam Properties Core density (㎏ / m ³ )22.523.022.621.521.221.3 Formability ¹¹⁾ OneOneOneOneOneOne Surface brittleness ¹²⁾ OneOneOneOneOneOne Breathable (ft ³ / min)2.61.01.01.01.31.6 Volatile Amount of Amine Catalyst (µg / g)≤1≤1≤11206090 Odor of foam ¹³⁾ AAAAAA
[519] week:
[520] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[521] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[522] 3) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[523] 4) Cat-A: 1-hydroxypropyl-2-methylimidazole (synthetic product)
[524] 5) Cat-B: N, N-dimethylpropanediamine (reagent, Kanto Chemical Co., Ltd.)
[525] 6) Cat-C: N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) propanediamine (synthetic)
[526] 7) Cat-D: N, N-dimethyl-1-hexanolamine (reagent, manufactured by Tokyo Chemical Co., Ltd.)
[527] 8) Cat-E: N- (2-hydroxypropyl) -N, N ', N ", N"'-tetramethyldimethylenetriamine (synthetic)
[528] 9) Cat-F: 2-((2- (2- (dimethylamino) ethoxy) ethyl) methylamino) ethanol) (Texacat-ZF10 from Huntsman)
[529] 10) Silicone foam stabilizer L580 made in Japan Unicar
[530] 11) Evaluation of moldability:
[531] The size of cracks in the foam was observed and classified into the following five steps.
[532] 1: almost none
[533] 2: small
[534] 3: medium
[535] 4: large
[536] 5: very large
[537] 12) Evaluation of surface brittleness:
[538] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[539] 1: not peeled off at all
[540] 2: slightly peeled off
[541] 3: medium
[542] 4: much peeling off
[543] 5: Peeling from surface to depth of 1 cm or more.
[544] 13) The odor of the foam:
[545] A: Almost no odor
[546] B: Slightly bad smell
[547] C: There is a bad smell
[548] D: Has strong odor
[549] Comparative Example 27Comparative Example 28Comparative Example 29Comparative Example 30Comparative Example 31Comparative Example 32 Formula (part by weight) Polyol (A) ¹⁾ 100 100 Polyol (B) ²⁾ 100 100Polyol (C) ³⁾ 100 100 Isocyanate ⁴⁾ 59.959.959.959.959.959.9 Cat-A ⁵⁾ 0.80.80.8 Cat-B ⁶⁾0.60.60.6 water5.05.05.05.05.05.0 Foam stabilizer ⁷⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time98129812 Rise time10098110105100118 Foam Properties Core density (㎏ / m ³ )25.321.225.824.621.326.5 Formability ⁸⁾ OneOne33One3 Surface brittleness ⁹⁾ OneOne23One3 Breathable (ft ³ / min)3.40.30.21.3≤0.1≤0.1 Volatile Amount of Amine Catalyst (µg / g)≤1≤1≤1≤1≤1≤1 Odor of the foam ¹⁰⁾ AAAAAA
[550] week:
[551] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[552] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[553] 3) Polyether polyol (C): A polyether polyol having a hydroxyl value of 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin. (GP3000 made by Sanyo Hwaseong company)
[554] 4) T-80: Japanese toluene diisocyanate
[555] 5) 1-hydroxypropyl-2-methylimidazole (synthetic product)
[556] 6) N, N-dimethylpropanediamine (Reagent, Kanto Chemical Co., Ltd.)
[557] 7) Silicone foam stabilizer L580 made in Japan Unicar
[558] 8) Evaluation of moldability:
[559] The size of cracks in the foam was observed and classified into the following five steps.
[560] 1: almost none
[561] 2: small
[562] 3: medium
[563] 4: large
[564] 5: very large
[565] 9) Evaluation of Surface Brittleness:
[566] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[567] 1: not peeled off at all
[568] 2: slightly peeled off
[569] 3: medium
[570] 4: much peeling off
[571] 5: Peeling from surface to depth of 1 cm or more.
[572] 10) Odor of the foam:
[573] A: Almost no odor
[574] B: Slightly bad smell
[575] C: There is a bad smell
[576] D: Has strong odor
[577] Comparative Example 33Comparative Example 34Comparative Example 35Comparative Example 36Comparative Example 37Comparative Example 38 Formula (part by weight) Polyol (A) ¹⁾ 100 100 Polyol (B) ²⁾ 100 100Polyol (C) ³⁾ 100 100 Isocyanate ⁴⁾ 59.959.959.959.959.959.9 Cat-C ⁵⁾ 1.01.01.0 Cat-D ⁶⁾0.80.80.8 water5.05.05.05.05.05.0 Foam stabilizer ⁷⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time98129812 Rise time10098110105100118 Foam Properties Core density (㎏ / m ³ )23.921.424.624.621.326.5 Formability ⁸⁾ 3One33One3 Surface brittleness ⁹⁾ 3One43One4 Breathable (ft ³ / min)1.90.10.21.5≤0.1≤0.1 Volatile Amount of Amine Catalyst (µg / g)≤1≤1≤1123125120 Odor of the foam ¹⁰⁾ AAAAAA
[578] week:
[579] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[580] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[581] 3) Polyether polyol (C): A polyether polyol having a hydroxyl value of 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin. (GP3000 made by Sanyo Hwaseong company)
[582] 3) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[583] 5) N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) propanediamine (synthetic)
[584] 6) N, N-dimethyl-1-hexanamine (reagent, manufactured by Tokyo Chemical Co., Ltd.)
[585] 7) Silicone foam stabilizer L580 made in Japan Unicar
[586] 8) Evaluation of moldability:
[587] The size of cracks in the foam was observed and classified into the following five steps.
[588] 1: almost none
[589] 2: small
[590] 3: medium
[591] 4: large
[592] 5: very large
[593] 9) Evaluation of Surface Brittleness:
[594] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[595] 1: not peeled off at all
[596] 2: slightly peeled off
[597] 3: medium
[598] 4: much peeling off
[599] 5: Peeling from surface to depth of 1 cm or more.
[600] 10) Odor of the foam:
[601] A: Almost no odor
[602] B: Slightly bad smell
[603] C: There is a bad smell
[604] D: Has strong odor
[605] Comparative Example 39Comparative Example 40Comparative Example 41Comparative Example 42Comparative Example 43Comparative Example 44 Formula (part by weight) Polyol (A) ¹⁾ 100 100 Polyol (B) ²⁾ 100 100Polyol (C) ³⁾ 100 100 Isocyanate ⁴⁾ 59.959.959.959.959.959.9 Cat-C ⁵⁾ 0.40.40.40.4 Cat-D ⁶⁾ 0.180.180.18 Cat-E ⁷⁾0.150.150.15 water5.05.05.05.05.05.0 Foam stabilizer ⁸⁾ 1.01.01.01.01.01.0 INDEX105105105105105105 Responsiveness (seconds) Cream time98109810 Rise time1059811010697111 Foam Properties Core density (㎏ / m ³ )23.220.424.623.320.225.1 Formability ⁹⁾ 3One33One3 Surface brittleness ¹⁰⁾ 3One43One4 Breathable (ft ³ / min)2.3≤0.10.12.4≤0.10.1 Volatile Amount of Amine Catalyst (µg / g)626060889395 Odor of the foam ¹¹⁾ AAAAAA
[606] week:
[607] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[608] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[609] 3) Polyether polyol (C): A polyether polyol having a hydroxyl value of 56 mg-KOH / g prepared by addition polymerization of only propylene oxide to glycerin. (GP3000 made by Sanyo Hwaseong company)
[610] 4) T-80: Japanese toluene diisocyanate
[611] 5) N, N-dimethyl-1-hexanamine (reagent, manufactured by Tokyo Chemical Co., Ltd.)
[612] 6) N- (2-hydroxypropyl) -N, N ', N ", N"'-tetramethyldimethylenetriamine (synthetic product)
[613] 7) 2-((2- (2- (dimethylamino) ethoxy) ethyl) methylamino) ethanol) (Huntsman (Texacat-ZF10 manufactured by Huntsman)
[614] 8) Silicone foam stabilizer L580 made in Japan Unicar Corporation
[615] 9) Evaluation of formability:
[616] The size of cracks in the foam was observed and classified into the following five steps.
[617] 1: almost none
[618] 2: small
[619] 3: medium
[620] 4: large
[621] 5: very large
[622] 10) Evaluation of surface brittleness:
[623] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[624] 1: not peeled off at all
[625] 2: slightly peeled off
[626] 3: medium
[627] 4: much peeling off
[628] 5: Peeling from surface to depth of 1 cm or more.
[629] 11) odor of the foam:
[630] A: Almost no odor
[631] B: Slightly bad smell
[632] C: There is a bad smell
[633] D: Has strong odor
[634] Comparative Example 45Comparative Example 46Comparative Example 47Comparative Example 48 Formula (part by weight) Polyol (A) ¹⁾ 60606060 Polyol (B) ²⁾ 40404040 Isocyanate ³⁾ 59.959.959.959.9 Cat-G ⁴⁾ 0.6 Cat-H ⁵⁾ 0.6 Cat-I ⁶⁾ 0.4Cat-J ⁷⁾2.0 water5.05.05.05.0 Foam stabilizer ⁸⁾ 1.01.01.01.0 INDEX105105105105 Responsiveness (seconds) Cream time99129 Rise time100105105115 Foam Properties Core density (㎏ / m ³ )23.222.822.924.9 Formability ⁹⁾ 22One5 Surface brittleness ¹⁰⁾ 32One5 Breathable (ft ³ / min)1.90.31.1- Volatile Amount of Amine Catalyst (µg / g)126014001180Odor of the foam ¹¹⁾ BCCD
[635] week:
[636] 1) Polyether polyol (A): Polyether polyol of hydroxyl value 56 mg-KOH / g synthesize | combined after making ethylene oxide react with glycerol, and then making propylene oxide react. Ethylene oxide ratio = 16%, terminal secondary OH ratio = 100%
[637] 2) Polyether polyol (B): A polyether polyol having a hydroxyl value of 56 mg-KOH / g synthesized by reacting glycerine with propylene oxide and then reacting with ethylene oxide. Ethylene oxide ratio = 20%, terminal primary OH ratio = 72.5%
[638] 3) T-80: Toluene diisocyanate made in Japan Polyurethane Co., Ltd.
[639] 4) N, N-dimethylethanolamine (Reagent, Kanto Chemical Co., Ltd.)
[640] 5) N, N, N-trimethyl-N'-hydroxyethyl-ethylenediamine (TOYOCAT-RX5 manufactured by Tosoh Corporation)
[641] 6) 33.3wt% dipropylene glycol solution of triethylenediamine (TEDA-L33 from Tosoh Corporation)
[642] 7) N-ethyl morpholine (a reagent product made by Kanto KK)
[643] 8) Silicone foam stabilizer L580 made in Japan Unicar Corporation
[644] 9) Evaluation of formability:
[645] The size of cracks in the foam was observed and classified into the following five steps.
[646] 1: almost none
[647] 2: small
[648] 3: medium
[649] 4: large
[650] 5: very large
[651] 10) Evaluation of surface brittleness:
[652] The condition of the surface of the foam was observed, and the degree of peeling off (surface brittleness) of the surface by hand was classified according to the following five grades.
[653] 1: not peeled off at all
[654] 2: slightly peeled off
[655] 3: medium
[656] 4: much peeling off
[657] 5: Peeling from surface to depth of 1 cm or more.
[658] 11) odor of the foam:
[659] A: Almost no odor
[660] B: Slightly bad smell
[661] C: There is a bad smell
[662] D: Has strong odor
[663] As apparent from Tables 8 to 12, according to the examples of the present invention, it is found that the moldability is good, the surface brittleness is not found, and a urethane foam having high air permeability is obtained. In addition, it can be seen that by using the catalyst of the present invention, the volatile amount of the amine catalyst is extremely small, and the odor of the foam is also reduced.
[664] On the contrary, as shown in Comparative Examples 27 to 44, even when the catalyst of the present invention was used, when the mixed polyol of the present invention was not used, a urethane foam having poor air permeability and a high density was obtained, thus meeting the market demand. You can see that you did not. In addition, as shown in Comparative Examples 45 to 46, when a reactive amine catalyst other than the catalyst of the present invention is used, when the scorch problem occurs because a urethane foam having poor moldability and a fairly brittle surface is obtained. There is also. Moreover, even if a reactive amine catalyst is used, an amine catalyst volatilizes from the foam obtained and the odor of foam itself produces. Therefore, these urethane foams become foams which are not suitable for the market demand.
[665] In addition, as shown in Comparative Examples 47 to 48, in the case of using a non-reactive amine catalyst other than the catalyst of the present invention, the volatility of the amine catalyst from the foam is increased, and there is a bad smell of the foam itself, which is suitable for the market demand. It is a form that is not.
[666] In the method for producing a flexible urethane foam, by using the formulation of the present invention, it is possible to form a foam having good moldability and high air permeability without using a tin catalyst.
[667] Since the flexible urethane foam obtained by this invention does not contain a highly toxic catalyst, it can use it in peace. In addition, the catalyst of the present invention has good storage stability even during premixing, and long-term storage, which has been difficult with a prescription using a conventional tin catalyst, has become possible.
[668] The amine catalyst used in the third embodiment of the present invention is a reactive catalyst, and it is possible to solve odor problems, fogging problems, and other problems of material contamination.

权利要求:
Claims (24)
[1" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, using a polyether polyol containing at least 5% by weight or more of oxyethylene groups (relative to the weight of the total polyol) in the chain and whose ends are sealed with secondary OH groups,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) As the catalyst, one or two or more compounds selected from the imidazole compounds represented by the following chemical formulas are used,
[Formula]
Wherein R 1, R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydroxymethyl group or a phenyl group; R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an aminopropyl group or dimethylamino A propyl group, benzyl group, vinyl group, aryl group, benzyl group, phenyl group, cyanoethyl group or a functional group represented by the following formula,
[Formula]
(Wherein R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3),
Method for producing a flexible polyurethane foam, characterized in that the tin-based catalyst is not used.
[2" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, a polyether polyol containing at least 5% by weight or more of oxyethylene groups (with respect to the weight of the total polyol) inside the chain and whose ends are sealed with secondary OH groups,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) As the catalyst, 1,2-dimethylimidazole, 1-methylimidazole, 1-n-butyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1- ( 3'-dimethylaminopropyl) -imidazole, 1- (3'-aminopropyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (2'-hydroxypropyl ) -2-methylimidazole, 1- (2'-hydroxyethyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole and 1- (2'-hydroxyethyl A method for producing a flexible polyurethane foam, characterized in that it uses at least one or two or more compounds selected from the group consisting of) -imidazole, and does not use a tin catalyst.
[3" claim-type="Currently amended] The method for producing a flexible polyurethane foam according to claim 1 or 2, wherein the polyether polyol has a hydroxyl value of 33 to 84 mg-KOH / g.
[4" claim-type="Currently amended] The process for producing a flexible polyurethane foam according to claim 1 or 2, wherein the polyol and polyisocyanate are reacted in the presence of a catalyst and a blowing agent.
[5" claim-type="Currently amended] The method of producing a flexible polyurethane foam according to claim 4, wherein the blowing agent is water, and the amount thereof is 2 to 8 parts by weight per 100 parts by weight of the polyol.
[6" claim-type="Currently amended] The method of claim 4, wherein the blowing agent is carbon dioxide.
[7" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a blowing agent,
(1) A polyol, containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) in the chain, the terminal being blocked by a secondary OH group, and having a hydroxyl value of 33 to 84 mg-KOH / g Using polyether polyols,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) As the catalyst, 1,2-dimethylimidazole, 1-methylimidazole, 1-n-butyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1- ( 3'-dimethylaminopropyl) -imidazole, 1- (3'-aminopropyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (2'-hydroxypropyl ) -2-methylimidazole, 1- (2'-hydroxyethyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, and 1- (2'-hydroxy Using at least one or two or more imidazole compounds selected from the group consisting of ethyl) -imidazole, without using a tin catalyst,
(4) A method for producing a flexible polyurethane foam, wherein water is used as a blowing agent and its amount is 2 to 8 parts by weight per 100 parts by weight of polyol.
[8" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol At least 5% by weight or more of the polyol chain terminal is used in combination with a polyether polyol (B) which is a primary OH group,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) As the catalyst, one or two or more selected from the group consisting of an imidazole compound represented by the following chemical formula, triethylenediamine and N-methyl-N '-(2-dimethylaminoethyl) piperazine Use,
[Formula]
(Wherein R 1, R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group; R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a vinyl group, an aryl group, A phenyl group and a cyanoethyl group.),
(4) A method for producing a flexible polyurethane foam, characterized in that no tin catalyst is used.
[9" claim-type="Currently amended] The method for producing a flexible polyurethane foam according to claim 8, wherein the polyether polyol (A) and the polyether polyol (B) each have a hydroxyl value of 33 to 84 mg-KOH / g.
[10" claim-type="Currently amended] The method for producing a flexible polyurethane foam according to claim 8 or 9, wherein the ratio of the polyether polyol (A) to the polyether polyol (B) is 10/90 to 90/10 based on the weight ratio.
[11" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol At least 5% by weight or more of the polyol chain terminal is used in combination with a polyether polyol (B) which is a primary OH group,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) 1 type selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 1-n-butyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole Or more than one imidazole compound is used as a catalyst,
(4) A method for producing a flexible polyurethane foam, characterized in that no tin catalyst is used.
[12" claim-type="Currently amended] 12. The composition according to any one of claims 8 to 11, which comprises one or two or more auxiliaries selected from the group consisting of blowing agents, foam stabilizers, crosslinkers or chain extenders, colorants, flame retardants and antioxidants. Process for producing a flexible polyurethane foam, characterized in that the reaction in the presence of additional.
[13" claim-type="Currently amended] 13. The process for producing a flexible polyurethane foam according to claim 12, wherein the blowing agent is water, and the amount thereof is 0.5 to 8 parts by weight per 100 parts by weight of the polyol.
[14" claim-type="Currently amended] The method of claim 12, wherein the blowing agent is carbon dioxide.
[15" claim-type="Currently amended] In the process for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a blowing agent,
(1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol To polyether polyol (B), wherein at least 5% by weight or more of the polyol chain ends are used as primary OH groups, and the ratio of polyether polyol (A) to polyether polyol (B) is based on 10 / 90-90 / 10,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) As catalyst, 1,2-dimethylimidazole, 1-methylimidazole, 1-n-butyl-2-methylimidazole, triethylenediamine and N-methyl-N '-(2-dimethyl Amino ethyl) piperazine using one or two or more selected from the group consisting of, without using a tin catalyst
(4) A process for producing a flexible polyurethane foam, characterized in that water is used as a blowing agent and its amount is 0.5-8 parts by weight per 100 parts by weight of polyol.
[16" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol At least 5% by weight of the polyol chain terminal is used in combination with a polyether polyol (B) which is a primary OH group,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) A compound represented by the following formula (1) as a catalyst:
[Formula 1]
Wherein R 1, R 2, and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a phenyl group, a benzyl group, a vinyl group, an allyl group, or a cyanoethyl group; R 4 is an amino propyl group , A dimethylaminopropyl group, or a substituent represented by the following formula,
[Formula]
Here, R5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3.)
Compound represented by the following formula (2):
[Formula 2]
Wherein R 6 and R 7 independently represent an alkyl group having 1 to 4 carbon atoms, a dimethylaminopropyl group or a diethylaminopropyl group, and R 6 and R 7 are each bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R8 represents an alkylene group having 2 to 16 carbon atoms.
Compound represented by the following formula (3):
[Formula 3]
Herein, R9 and R10 independently represent an alkyl group having 1 to 4 carbon atoms, dimethylaminopropyl group or diethylaminopropyl group, and R9 and R10 may be bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R 11 represents an alkylene group having 3 to 16 carbon atoms, R 12 represents an alkylene group having 2 to 3 carbon atoms, m 1 represents an integer of 0 to 2, R 13 represents an alkyl group having 1 to 4 carbon atoms, or the following: A substituent represented by the chemical formula of
[Formula]
Here, R12 and m1 are defined as above.)
Compound represented by the following formula (4):
[Formula 4]
(In this case, R14 and R15 independently represent an alkyl group having 1 to 4 carbon atoms, dimethylaminopropyl group or diethylaminopropyl group, and R14 and R15 may be bonded directly or through a nitrogen atom or an oxygen atom to form a ring structure. R16 represents an alkylene group having 3 to 16 carbon atoms.
Compound represented by the following formula (5):
[Formula 5]
(R 17, R 18, and R 19 independently represent an alkyl group having 1 to 4 carbon atoms, R 20 represents a hydrogen atom or a methyl group, and m 2 represents an integer of 1 to 3.)
In addition, using one or two or more compounds selected from the group consisting of compounds represented by the following formula (6),
[Formula 6]
(Herein, R21, R22, and R23 represent an alkyl group having 1 to 4 carbon atoms; R24 represents a hydrogen atom or a methyl group; m3 and n represent an integer of 1 to 3.)
(4) A method for producing a flexible polyurethane foam, characterized by not using a tin catalyst.
[17" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol At least 5% by weight of the polyol chain terminal is used in combination with a polyether polyol (B) which is a primary OH group,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) 1- (3'aminopropyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxypropyl) -imidazole, 1- (2'-hydroxyethyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, N, N ' -Dimethylpropanediamine, N, N-dimethyl-N ', N'-bis (hydroxyethyl) propanediamine, N, N-dimethyl-N'N'-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-1-hexanol-amine, N- (2-hydroxypropyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, 2-((2- (2-di- At least one compound selected from the group consisting of methylaminoethoxy) ethyl) methylamino) ethanol and 1-((2- (2-dimethylamino) ethoxy) -ethyl) methylamino) -2-propanol Used as a catalyst,
(4) A method for producing a flexible polyurethane foam, characterized by not using a tin catalyst.
[18" claim-type="Currently amended] The process for producing a flexible polyurethane foam according to claim 16 or 17, wherein the polyether polyol (A) and the polyether polyol (B) each have a hydroxyl value of 33 to 84 mg-KOH / g.
[19" claim-type="Currently amended] The flexible polyurethane foam according to any one of claims 16 to 18, wherein the ratio of the polyether polyol (A) to the polyether polyol (B) is 10/90 to 90/10 based on the weight ratio. Manufacturing method.
[20" claim-type="Currently amended] The reaction according to any one of claims 16 to 19, wherein the reaction is carried out in the presence of one or two or more additional auxiliaries selected from the group consisting of blowing agents, foam stabilizers, crosslinkers or chain extenders, colorants, flame retardants and antioxidants. Method for producing a flexible polyurethane foam, characterized in that carried out.
[21" claim-type="Currently amended] 21. The method of claim 20, wherein the blowing agent is water, the amount of which is 0.5 to 8 parts by weight per 100 parts by weight of the polyol.
[22" claim-type="Currently amended] 21. The method of claim 20, wherein the blowing agent is carbon dioxide.
[23" claim-type="Currently amended] 23. The process for producing a flexible polyurethane foam according to any one of claims 16 to 22, wherein the flexible polyurethane foam is a flexible slab foam or a hot mold foam.
[24" claim-type="Currently amended] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst,
(1) As a polyol, a polyether polyol (A) containing at least 5% by weight or more of an oxyethylene group (relative to the weight of the total polyol) inside the polyol chain and whose terminal is sealed with a secondary OH group, and the weight of the total polyol To polyether polyol (B), wherein at least 5% by weight or more of the polyol chain ends are used as primary OH groups, and the ratio of polyether polyol (A) to polyether polyol (B) is based on 10 / 90-90 / 10,
(2) Toluene diisocyanate and / or its derivative is used as polyisocyanate,
(3) As the catalyst, 1- (3'aminopropyl) -2-methylimidazole, 1- (3'-aminopropyl) -imidazole, 1- (2'-hydroxypropyl) -2-methyl Midazole, 1- (2'-hydroxypropyl) -imidazole, 1- (2'-hydroxyethyl) -imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, N , N'-dimethylpropanediamine, N, N-dimethyl-N ', N'-bis (hydroxyethyl) propanediamine, N, N-dimethyl-N'N'-bis (2-hydroxypropyl) propanediamine , N, N-dimethyl-1-hexanol-amine, N- (2-hydroxypropyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, 2-((2- (2 1 or 2 selected from the group consisting of -di-methylaminoethoxy) ethyl) methylamino) ethanol, and 1-((2- (2-dimethylamino) ethoxy) -ethyl) methylamino) -2-propanol Paper or more compounds, no tin catalyst,
(4) A method for producing a flexible polyurethane foam, wherein water is used as a blowing agent and its amount is 0.5 to 8 parts by weight per 100 parts by weight of polyol.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-10-31|Priority to JP2001334986A

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2001-10-31|Priority to JPJP-P-2001-00334986

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2002-02-15|Priority to JP2002038485A

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2002-02-15|Priority to JPJP-P-2002-00038485

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2002-06-25|Priority to JPJP-P-2002-00185084

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2002-06-25|Priority to JP2002185084A

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2002-10-30|Application filed by 토소가부시키가이샤

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2003-05-09|Publication of KR20030036060A

优先权:

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申请号 | 申请日 | 专利标题

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JP2001334986A|JP3969058B2|2001-10-31|2001-10-31|Method for producing flexible polyurethane foam|

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JPJP-P-2001-00334986|2001-10-31|

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JP2002038485A|JP2003238642A|2002-02-15|2002-02-15|Method for manufacturing flexible polyurethane foam|

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JPJP-P-2002-00038485|2002-02-15|

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JP2002185084A|JP2004027010A|2002-06-25|2002-06-25|Method for producing flexible polyurethane foam|

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JPJP-P-2002-00185084|2002-06-25|