JP5560553B2 - Amine catalyst composition for producing polyurethane resin and method for producing polyurethane resin using the same - Google Patents

Description

  The present invention relates to an amine catalyst composition for producing a polyurethane resin and a method for producing a polyurethane resin using the same. The catalyst composition of the present invention is extremely useful as a catalyst for producing a polyurethane resin having almost no volatile amine catalyst or harmful metal catalyst during the production of the polyurethane resin.

  The polyurethane resin is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially when used alone or in combination.

  In the production of polyurethane foam using water and / or a low-boiling organic compound as a foaming agent, among these catalysts, tertiary amine compounds are widely used because of their excellent productivity and moldability. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N , N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like. For example, refer nonpatent literature 1).

  In addition, as the metal compound, for example, an organometallic compound such as an organotin compound is often used. However, in most cases, it is used in combination with a tertiary amine catalyst because productivity and moldability deteriorate. Many are not used alone.

  Since the above-mentioned tertiary amine compound is gradually discharged from the polyurethane product as a volatile amine, for example, in automobile interior materials, etc., it causes odor problems due to the volatile amine, or PVC discoloration of an automotive instrument panel. In addition, fogging of the window glass due to migration of volatile components from the polyurethane product (foam) is caused. Further, the tertiary amine catalyst generally has a strong bad odor, and the working environment during the production of the polyurethane resin is significantly deteriorated.

  As a method for solving these problems, in place of the above-described volatile tertiary amine catalyst, an amine catalyst having a hydroxy group capable of reacting with polyisocyanate or a primary and secondary amino group in the molecule (hereinafter referred to as “the following”) And a method using a bifunctional crosslinking agent having a tertiary amino group in the molecule has been proposed (for example, see Patent Documents 1 to 5).

  The method using the above reactive catalyst is said to be able to avoid the above problem because it is immobilized in the polyurethane resin skeleton in a form reacted with polyisocyanate. Although this method is certainly effective in reducing the odor of the final resin product, these reactive catalysts have a problem in that the curability is lowered because the activity of the resinification reaction (reaction between polyol and isocyanate) is inferior. is there.

  The method using the above-mentioned crosslinking agent is effective in reducing the odor of the final resin product and improving the working environment when producing the polyurethane resin, but the physical properties such as hardness of the polyurethane resin are insufficient.

  Furthermore, a method of using an amine compound having a hydroxy group, a primary amino group and a secondary amino group in the molecule as a catalyst for producing a rigid polyurethane foam has been proposed (see, for example, Patent Document 6 and Patent Document 7). These methods are intended to improve the fluidity and thermal conductivity of the foam and have not been studied at all for improving the odor problem.

  On the other hand, the metal compound does not cause the odor problem and the problem of degrading other materials like the above-mentioned tertiary amine compound. However, when the metal compound is used alone, as described above, the productivity and physical properties are improved. In addition, the formability has deteriorated, and environmental problems due to heavy metals remaining in the product have been taken up.

JP-A-46-4846 Japanese Patent Publication No. 61-31727 Japanese Patent No. 2971979 Japanese Unexamined Patent Publication No. 63-265909 JP 2008-45113 A JP 2003-82051 A JP 2003-105051 A Keiji Iwata "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. 118

  The present invention has been made in view of the above-described background art, and its purpose is to provide a novel catalyst composition capable of obtaining polyurethane products with good productivity and moldability without causing odor problems and environmental problems, and It is to provide a method for producing a polyurethane resin using the same.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a triethylenediamine having a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group in the molecule as a catalyst for producing a polyurethane resin, and a tertiary class It has been found that when an amine compound is used in combination, a polyurethane product can be obtained without causing odor problems, toxicity and environmental problems, and the present invention has been completed.

  That is, the present invention is a polyurethane resin production catalyst composition as shown below and a polyurethane resin production method using the same.

  [1] The following general formula (1)

［式中、Ｘは、ヒドロキシ基、ヒドロキシメチル基、又はヒドロキシエチル基を表す。］
で示されるアミン化合物と、［泡化反応速度定数／樹脂化反応速度定数］の値が０．５以上の第３級アミン化合物とを含有するポリウレタン樹脂製造用の触媒組成物。

[Wherein, X represents a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group. ]
And a tertiary amine compound having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more, a catalyst composition for producing a polyurethane resin.

  [2] The catalyst composition for producing a polyurethane resin according to the above [1], wherein the amine compound represented by the general formula (1) is 2-hydroxymethyltriethylenediamine.

  [3] The tertiary amine compound is triethanolamine, bisdimethylaminoethyl ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N-dimethylamino. Ethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol and N, N, N′-trimethyl-N′- The catalyst composition for producing a polyurethane resin according to the above [1] or [2], characterized by (2-hydroxyethyl) bis (2-aminoethyl) ether.

  [4] The mixing ratio of the amine compound represented by the general formula (1) and the tertiary amine compound is [amine compound represented by the general formula (1)] / [tertiary amine compound] = 1. The catalyst composition for producing a polyurethane resin according to any one of the above [1] to [3], which is / 30 to 30/1 (weight ratio).

  [5] A method for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition according to any one of [1] to [4].

  [6] The above [1], wherein the catalyst composition according to any one of [1] to [4] is used in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyol. 5].

  The catalyst composition of the present invention can produce polyurethane products with good productivity and moldability.

  And since the polyurethane resin manufactured using the catalyst composition of this invention has almost no amine volatilized from a polyurethane resin, the PVC discoloration of the instrument panel for motor vehicles resulting from the conventional tertiary amine compound, and polyurethane It is effective for preventing fogging phenomenon of window glass due to migration of volatile components from foam.

  Hereinafter, the present invention will be described in more detail.

  The catalyst composition for producing a polyurethane resin of the present invention comprises an amine compound represented by the general formula (1) and a tertiary amine having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more. Compound.

  In the present invention, examples of the amine compound represented by the general formula (1) include hydroxytriethylenediamine, hydroxymethyltriethylenediamine, hydroxyethyltriethylenediamine, and the like. Hydroxymethyltriethylenediamine is preferred.

  The compound represented by the general formula (1) can be produced by a known method. For example, it can be produced by reacting a dibromocarboxylic acid ester corresponding to piperazine at an appropriate molar ratio and reducing the resulting ester.

  The tertiary amine compound used in the catalyst composition of the present invention is not particularly limited as long as the value of [foaming reaction rate constant / resinization reaction rate constant] is a tertiary amine compound of 0.5 or more.

  In the present invention, the resinification reaction rate constant (k1w) is a parameter calculated by the following method.

  That is, toluene diisocyanate and diethylene glycol were charged so that the molar ratio of isocyanate group / hydroxyl group was 1.0, a fixed amount of a tertiary amine compound was added as a catalyst, and the reaction was carried out at a constant temperature in a benzene solvent. The amount of unreacted isocyanate is measured. Here, assuming that the reaction between toluene diisocyanate and diethylene glycol is first-order at each concentration, the following equation holds.

dx / dt = k (ax) ² (2)
x: concentration of reacted NCO group (mol / L)
a: Initial concentration of NCO group (mol / L)
k: Reaction rate constant (L / mol · h)
t: Reaction time (h).

  Substituting the initial conditions t = 0 and X = 0 into the above equation (2) and integrating, the following equation is established.

1 / (ax) = kt + 1 / a (3)
The reaction rate constant k is obtained from the above equation (3), and is substituted into the following equation (4) to obtain the catalyst constant Kc.

k = ko + KcC (4)
ko: Non-catalytic reaction rate constant (L / mol · h)
Kc: catalyst constant (L ² / g · mol · h)
C: Catalyst concentration (mol / L) of the reaction system.

The obtained catalyst constant Kc is divided by the molecular weight of the catalyst to obtain a resination reaction rate constant k1w (L ² / g · mol · h) that can be regarded as an activity capacity per weight (see the following formula).

Kc / mc = k1w (5)
On the other hand, the foaming reaction constant (k2w) is obtained in the same manner as described above by reacting toluene diisocyanate and water in a benzene solvent under the same conditions as in the above-mentioned resinification reaction.

  Examples of the tertiary amine compound having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more include triethanolamine, bisdimethylaminoethyl ether, N, N, N ′, N ", N" -pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminoethyl-N'-methylamino Examples include ethyl-N ″ -methylaminoisopropanol and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether.

  The tertiary amine compound used in the catalyst composition of the present invention can be easily produced by methods known in the literature. For example, a method by reaction of diol and diamine, amination of alcohol, a method by reductive methylation of monoamino alcohol or diamine, a method by reaction of amine compound and alkylene oxide, and the like can be mentioned.

  In the present invention, the mixing ratio of the amine compound represented by the general formula (1) and the tertiary amine compound is not particularly limited, but the amine compound represented by the general formula (1); The mixing ratio is adjusted so that the weight ratio of the tertiary amine compound ([amine compound represented by the general formula (1)] / [tertiary amine compound]) is usually in the range of 1/30 to 30/1. Adjust. More preferably, it is in the range of 1 / 20-20 / 1. If the weight ratio exceeds this range, the synergistic effect of both catalysts may not be obtained, and satisfactory performance may not be exhibited in terms of physical properties and catalytic activity of the polyurethane resin.

  In the present invention, the amine compound represented by the general formula (1) and the tertiary amine compound used as the catalyst composition may be added in advance during the reaction, or may be added during the reaction. You may add simultaneously. Moreover, when mixing them, it can also be melt | dissolved and used for a solvent. Although it does not specifically limit as a solvent, For example, alcohol, such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, and 2-methyl-1,3-propanediol, toluene, xylene, mineral terpene, Hydrocarbons such as mineral spirits, esters such as ethyl acetate, butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide Examples include solvable organic solvents such as amides, β-diketones such as acetylacetone and fluorinated substituents thereof, chelating solvents such as ketoesters such as methyl acetoacetate and ethyl acetoacetate, and water. .

  Next, the manufacturing method of the polyurethane resin of this invention is demonstrated.

  The method for producing a polyurethane resin of the present invention comprises reacting a polyol and an isocyanate in the presence of the above-described catalyst composition of the present invention and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. Its features.

  In the method for producing a polyurethane resin of the present invention, the amount of the catalyst composition of the present invention is usually in the range of 0.01 to 30 parts by weight, preferably 0.1 to 100 parts by weight of the polyol used. It is in the range of ˜20 parts by weight. If the amount is less than 0.01 parts by weight, the effect of the catalyst may not be obtained. On the other hand, when it exceeds 30 parts by weight, not only the effect of increasing the catalyst is not obtained, but also the physical properties of the polyurethane resin may be deteriorated.

  In the method for producing a polyurethane resin of the present invention, examples of the polyol used include conventionally known polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. . These polyols can be used alone or in combination as appropriate.

  In the method for producing a polyurethane resin of the present invention, the polyether polyol to be used is not particularly limited, but for example, a compound having at least two active hydrogen groups (ethylene glycol, propylene glycol, glycerin, triglyceride). Examples include polyhydric alcohols such as methylolpropane and pentaerythritol, amines such as ethylenediamine, alkanolamines such as ethanolamine and diethanolamine, etc.) as starting materials and alkylene oxides (such as ethylene oxide and propylene oxide) (For example, Gunter Oertel, “Polyurethane Handbook” (1985) Hans Publisher). Company (Germany), p. See method according to 42-53].

  In the method of the present invention, the polyester polyol to be used is not particularly limited, and examples thereof include those obtained from the reaction of dibasic acid and glycol, wastes from the production of nylon, trimethylolpropane, and pentaerythritol. Wastes of phthalic polyester, polyester polyols obtained by treating and inducing waste products [for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. See description of 117. ].

  In the method for producing a polyurethane resin of the present invention, the polymer polyol to be used is not particularly limited. For example, the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.). ) In the presence of a radical polymerization catalyst.

  In the method for producing a polyurethane resin of the present invention, the flame retardant polyol used is not particularly limited. For example, a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, epichlorohydrin, or trichlorobutylene. Examples thereof include halogen-containing polyols and phenol polyols obtained by ring-opening polymerization of oxides.

  In the method for producing a polyurethane resin of the present invention, a polyol having an average hydroxyl value in the range of 20 to 1000 mgKOH / g can be used. For a soft polyurethane resin or a semi-rigid polyurethane resin, an average hydroxyl value in the range of 20 to 100 mgKOH / g. As the hard polyurethane resin, those having an average hydroxyl value in the range of 100 to 800 mgKOH / g are preferably used.

  The polyisocyanate used in the present invention is not particularly limited as long as it is a conventionally known polyisocyanate. For example, toluene diisocyanate (hereinafter sometimes referred to as TDI), diphenylmethane diisocyanate (hereinafter referred to as MDI). ), Aromatic polyisocyanates such as naphthylene diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate, and the like And the like. Among these, TDI and its derivatives, or MDI and its derivatives are preferable, and these may be used alone or in combination.

  Examples of TDI and derivatives thereof include a mixture of 2,4-TDI and 2,6-TDI, a terminal isocyanate prepolymer derivative of TDI, and the like. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate, and a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  Among these isocyanates, TDI and its derivatives and / or MDI and its derivatives are preferably used for soft polyurethane resins and semi-rigid polyurethane resin products. As the rigid polyurethane resin, a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate is preferably used.

  The mixing ratio of these polyisocyanates and polyols is not particularly limited, but when expressed in terms of isocyanate index ([isocyanate group] / [active hydrogen group capable of reacting with isocyanate groups]), generally the range is 60 to 400. preferable.

  In the method for producing a polyurethane resin of the present invention, as a catalyst, an amine compound represented by the above general formula (1), and a tertiary having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more In addition to the catalyst composition of the present invention containing an amine compound, other organometallic catalysts, carboxylic acid metal salt catalysts, tertiary amine catalysts, and quaternary ammonium salts are used without departing from the spirit of the present invention. A catalyst may be used in combination.

  The organometallic catalyst is not particularly limited as long as it is a conventionally known one. For example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diester Examples include acetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, and the like.

  The carboxylic acid metal salt catalyst may be any conventionally known one, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  The tertiary amine catalyst may be a conventionally known one, and is not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetra Methylpropylenediamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 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, N′-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, - ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, tertiary amine compounds such as 1-dimethylamino-propyl imidazole.

  The quaternary ammonium salt catalyst may be a conventionally known one, and is not particularly limited. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium water such as tetramethylammonium hydroxide salts, and the like. Examples thereof include tetraalkylammonium organic acid salts such as oxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  In the method for producing a polyurethane resin of the present invention, the catalyst composition of the present invention can be used alone or mixed with the above-mentioned other catalysts. For mixing adjustment, if necessary, dipropylene glycol, A solvent such as ethylene glycol, 1,4-butanediol or water can be used. The amount of the solvent is not particularly limited, but is preferably 3 times or less by weight based on the total amount of the catalyst. If it exceeds 3 times by weight, the physical properties of the resulting foam may be affected, and it is not preferable for economic reasons. The catalyst composition thus adjusted may be used by adding to the polyol, or individual components may be added separately to the polyol, and there is no particular limitation.

  In the method for producing a polyurethane resin of the present invention, a foaming agent can be used if necessary. The foaming agent is not particularly limited, and examples thereof include 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3-heptafluoro Fluorocarbon compounds such as propane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low boiling point hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, and acetone, and a mixture is used. be able to. As the low-boiling hydrocarbons, hydrocarbons having a boiling point of usually −30 to 70 ° C. are usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane, and mixtures thereof.

The amount of the foaming agent used is determined according to the desired density and foam physical properties. Specifically, the foam density obtained is usually 5 to 1000 kg / m ³ , preferably 10 to 500 kg / m ^3. Selected as

  In the method for producing a polyurethane resin of the present invention, a surfactant can be used as a foam stabilizer if necessary. Examples of the surfactant to be used include conventionally known organosilicone surfactants, and specifically, nonionic systems such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Surfactant or a mixture thereof is exemplified. Their use amount is usually 0.1 to 10 parts by weight per 100 parts by weight of polyol.

  In the method for producing a polyurethane resin of the present invention, a crosslinking agent or a chain extender can be used if necessary. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine and xylylene. Examples include polyamines such as range amine and methylene bisorthochloroaniline.

  In the method for producing a polyurethane resin of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant used include reactive flame retardants such as phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl Tertiary phosphates such as phosphate, halogen-containing tertiary phosphates such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, halogens such as dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A Examples include organic compounds, inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount is not particularly limited and varies depending on the required flame retardancy, but is usually 4 to 20 parts by weight with respect to 100 parts by weight of the polyol.

  In the method for producing a polyurethane resin of the present invention, if necessary, a colorant, an antioxidant, and other conventionally known additives can be used. The type and amount of these additives may be within the normal usage range of the additive used.

  The method for producing the polyurethane resin of the present invention is carried out by rapidly mixing and stirring the mixed solution in which the raw materials are mixed, and then injecting the mixture into a suitable container or mold to perform foam molding. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, high-pressure, low-pressure and spray-type devices can be used.

  Examples of polyurethane resin products include elastomers that do not use a foaming agent, polyurethane foams that use a foaming agent, and the like, and the method for producing a polyurethane resin of the present invention is suitably used for producing such polyurethane foam products. .

  Examples of polyurethane foam products include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, etc. The polyurethane resin production method of the present invention is a flexible polyurethane foam car sheet used as an automobile interior material, semi-rigid polyurethane. It is particularly preferably used for the production of insulation panels made of foam instrument panels and handles and rigid polyurethane foam.

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

The semi-rigid polyurethane foam is a reversibly deformable foam having an open cell structure and high air permeability like the flexible polyurethane foam, although the foam density and compressive strength are higher than those of the flexible polyurethane foam. Oertel, "Polyurethane Handbook" (1985 edition) Hanser Publishers (Germany), p. 223-233, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 211-221. ]. Moreover, since the polyol and isocyanate raw material to be used are the same as that of the flexible polyurethane foam, it is generally classified as a flexible polyurethane foam. The physical properties of the semi-rigid urethane foam are not particularly limited, but generally, the density is 40 to 800 kg / m ³ , the compressive strength (ILD 25%) is 10 to 200 kPa, and the elongation is 40 to 200%. It is. In the present invention, the flexible polyurethane foam may include a semi-rigid polyurethane foam from the raw materials used and the physical properties of the foam.

Further, the rigid polyurethane foam refers to a foam having a highly crosslinked closed cell structure and cannot be reversibly deformed [Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany), p. 234-313, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 224-283. ]. The physical properties of the rigid urethane foam are not particularly limited, but are generally in the range of a density of 10 to 100 kg / m ³ and a compressive strength of 50 to 1000 kPa.

  Hereinafter, although demonstrated based on an Example and a comparative example, this invention is not limitedly interpreted only to these Examples.

(Calculation of resinification reaction rate constant)
Reference Example 1
In a 200 ml Erlenmeyer flask purged with nitrogen, 50 ml of DEG-containing benzene solution prepared so that the concentration of diethylene glycol (DEG) is 0.15 mol / L is collected, and N, N, N ′, N ″, N ″ is collected in this. -60.7 mg (0.35 mmol) of pentamethyldiethylenetriamine (TOYOCAT-DT manufactured by Tosoh Corporation) was added to prepare a solution A.

  Next, 50 ml of a TDI-containing benzene solution prepared so that the concentration of 2,6-toluene diisocyanate (TDI) was 0.15 mol / L was collected in a 100 ml Erlenmeyer flask purged with nitrogen and used as solution B.

  The liquid A and the liquid B were each kept at 30 ° C. for 30 minutes, and then the liquid B was added to the liquid A and the reaction was started while stirring. About 10 ml of the reaction solution is collected every 10 minutes after the reaction starts, the unreacted isocyanate is reacted with an excess of di-n-butylamine (DBA) solution, and the remaining DBA is back titrated with 0.2 N hydrochloric acid ethanol solution. Thus, the amount of unreacted isocyanate was quantified.

As described above, the reaction rate constant k (L / mol · h) was determined on the assumption that the reaction between the isocyanate and alcohol (resinification reaction) was first-order at each concentration. Further, the rate constant Kc (L ² / eq · mol · h) per catalyst was obtained by dividing the reaction rate constant k by the catalyst concentration. Furthermore, the resination rate constant k1w (L ² / g · mol · h) that can be regarded as the activity capacity per weight was determined by dividing Kc by the molecular weight of the catalyst. The results are shown in Table 1.

参考例２〜参考例８．
触媒として表１に示した第３級アミン化合物を使用した以外は、参考例１と同様にして樹脂化反応速度定数ｋ１ｗを算出した。結果を表１にあわせて示す。

Reference Examples 2 to 8
The resination reaction rate constant k1w was calculated in the same manner as in Reference Example 1 except that the tertiary amine compound shown in Table 1 was used as the catalyst. The results are shown in Table 1.

(Calculation of foaming reaction rate constant)
Reference Example 9
In a 200 ml Erlenmeyer flask purged with nitrogen, 100 ml of a water-containing benzene solution prepared so that the concentration of water becomes 0.078 mol / L was collected, and this was collected with N, N, N ′, N ″, N ″ -pentamethyl. 60.7 mg (0.35 mmol) of diethylenetriamine (TOYOCAT-DT manufactured by Tosoh Corporation) was added to prepare A solution.

  Next, 10 ml of a TDI-containing benzene solution prepared so that the concentration of 2,6-toluene diisocyanate (TDI) was 0.78 mol / L was collected into a 100 ml Erlenmeyer flask purged with nitrogen, and used as solution B.

  The liquid A and the liquid B were each kept at 30 ° C. for 30 minutes, and then the liquid B was added to the liquid A and the reaction was started while stirring. About 10 ml of the reaction solution is collected every 10 minutes after the reaction starts, the unreacted isocyanate is reacted with an excess of di-n-butylamine (DBA) solution, and the remaining DBA is back titrated with 0.2 N hydrochloric acid ethanol solution. Thus, the amount of unreacted isocyanate was quantified.

As described above, the reaction rate constant k (L / mol · h) was determined on the assumption that the reaction between the isocyanate and water (foaming reaction) was first-order at each concentration. The rate constant Kc (L ² / eq · mol · h) per catalyst was determined by dividing the rate constant k by the catalyst concentration. Furthermore, k2w (L ² / g · mol · h) that can be regarded as the activity ability per weight was determined by dividing Kc by the molecular weight of the catalyst. The results are shown in Table 1.

Reference Example 10 to Reference Example 16
The foaming reaction rate constant k2w was calculated in the same manner as in Reference Example 9 except that the tertiary amine compound shown in Table 1 was used as the catalyst. The results are shown in Table 1.

(Calculation of foaming / resinization activity ratio)
From the results in Table 1, the ratio of foaming / resinization activity of the tertiary amine compound (= [resinization reaction rate constant k1w / foaming reaction rate constant k2w]) was determined. The results are also shown in Table 2.

合成例１．
２Ｌのセパラブルフラスコにピペラジン４３．１ｇ（０．５ｍｏｌ）、トリエチルアミン１５１．８ｇ（１．５ｍｏｌ）を仕込み、トルエンで希釈した。窒素置換後、これにトルエンで希釈した２，３−ジブロモプロピオン酸エチル（東京化成工業社製）を攪拌しながら添加し、１００℃で２４時間熟成反応を行った。析出したトリエチルアミンの塩酸塩をろ過により除去し、得られた反応液を濃縮し、エステル体を合成した。このエステル体をテトロヒドロフランに溶解させ、氷浴下、水素化アルミニウムリチウムのテトロヒドロフラン溶液に攪拌しながら添加した。室温で２時間反応後、水、１５％水酸化ナトリウム水溶液を加えて反応を停止し、不溶物をろ過により除去した。反応液を濃縮後、酢酸エチルで抽出洗浄した。酢酸エチルを除去し、目的化合物である２−ヒドロキシメチルトリエチレンジアミンを４８ｇ得た（収率６８％）。

Synthesis Example 1
Piperazine (43.1 g, 0.5 mol) and triethylamine (151.8 g, 1.5 mol) were charged into a 2 L separable flask and diluted with toluene. After substitution with nitrogen, ethyl 2,3-dibromopropionate (manufactured by Tokyo Chemical Industry Co., Ltd.) diluted with toluene was added to the mixture with stirring, and an aging reaction was carried out at 100 ° C. for 24 hours. The precipitated triethylamine hydrochloride was removed by filtration, and the resulting reaction solution was concentrated to synthesize an ester. This ester was dissolved in tetrohydrofuran and added to a tetrohydrofuran solution of lithium aluminum hydride with stirring in an ice bath. After reacting at room temperature for 2 hours, water and 15% aqueous sodium hydroxide solution were added to stop the reaction, and insoluble materials were removed by filtration. The reaction mixture was concentrated and extracted and washed with ethyl acetate. Ethyl acetate was removed to obtain 48 g of 2-hydroxymethyltriethylenediamine as the target compound (yield 68%).

Example 1.
A premix A was prepared using the polyol, cell opener, cross-linking agent, foam stabilizer, and water at the raw material mixing ratio shown in Table 3.

  Take 148.1 g of Premix A in a 500 ml polyethylene cup, and use 2-hydroxymethyltriethylenediamine and 70% dipropylene glycol solution (produced by Tosoh Corporation, TOYOCAT-ET) synthesized in Synthesis Example 1 as a catalyst. The mixture was added at the blending ratio shown in Table 2, and the temperature was adjusted to 20 ° C.

  In a separate container, the isocyanate liquid whose temperature is adjusted to 20 ° C. is added in an amount in which the isocyanate index [= isocyanate group / OH group (molar ratio) × 100] is 100 in a premix A cup, and quickly stirred with a stirrer. Stir at 6000 rpm for 5 seconds.

  The mixed and stirred liquid mixture was transferred to a 2 liter polyethylene cup whose temperature was adjusted to 60 ° C., and the reactivity during foaming was measured. Moreover, foam density was measured and compared from the obtained molded foam. The results are shown in Table 4.

  The measurement method for each measurement item is as follows.

(1) Measurement items for reactivity.
Cream time: Visually measure foaming start time, foam start time,
Gel time: Measures the time required for the reaction to progress to a resinous material from a liquid
Rise time: Measure the time when the rising of the foam stops visually.

(2) Foam Core Density The core density was calculated by cutting the center part of the molded foam into a size of 7 × 7 × 5 cm and measuring the size and weight accurately.

(3) Foam odor A 5 × 5 × 5 cm size foam was cut from the foam whose foam core density was measured, put into a mayonnaise bottle, and capped. After the bottle was heated at 80 ° C. for 1 hour, the bottle was cooled to room temperature, the smell of the foam was smelled on 10 monitors, and the intensity of the smell was evaluated as follows.

◎: almost no smell,
○: Slightly
Δ: Odor
X: There is a strong odor.

実施例２〜６、参考例１７〜２２．
ビス（ジメチルアミノエチル）エーテルの代わりに表４に示したアミン化合物を使用した以外は、実施例１と同じ手法を用いた。結果を表４にあわせて示す。

Examples 2 to 6, Reference Examples 17 to 22 .
The same procedure as in Example 1 was used except that the amine compound shown in Table 4 was used instead of bis (dimethylaminoethyl) ether. The results are shown in Table 4.

Examples 1 to 6 are examples in which the catalyst composition of the present invention was used. As is apparent from Table 4, all of the catalytic activities were high, and the odor of the amine catalyst was scarce from the obtained foam. .

Comparative Example 1 and Comparative Example 2
The same procedure as in Example 1 was used except that the amine compound shown in Table 5 was used instead of bis (dimethylaminoethyl) ether. The results are shown in Table 5.

比較例３．
触媒として合成例１で合成した２−ヒドロキシメチルトリエチレンジアミンを単独で使用した以外は、実施例１と同じ手法を用いた。結果を表５にあわせて示す。

Comparative Example 3
The same procedure as in Example 1 was used except that 2-hydroxymethyltriethylenediamine synthesized in Synthesis Example 1 was used alone as a catalyst. The results are shown in Table 5.

Comparative Example 4 to Comparative Example 6.
The same technique as in Example 1 was used, except that triethylenediamine (manufactured by Tosoh Corporation, TEDA-L33) was used instead of 2-hydroxymethyltriethylenediamine. The results are shown in Table 5.

  As is apparent from Table 5, when a tertiary amine compound having a value of [foaming reaction rate constant / resinization reaction rate constant] smaller than 0.5 (Comparative Example 1, Comparative Example 2), The amount of catalyst used increased and the odor of the amine catalyst was confirmed from the foam. For this reason, the PVC discoloration of the automotive instrument panel caused by the amine catalyst and the fogging phenomenon of the window glass cannot be prevented.

  In addition, when 2-hydroxymethyltriethylenediamine is used alone (Comparative Example 3), it is possible to reduce the odor of the amine catalyst from the obtained foam, but the foam time is slow and the foam is obtained with good productivity. I could not.

  On the other hand, without using 2-hydroxymethyltriethylenediamine, a 33.3% dipropylene glycol solution (TEDA-L33, manufactured by Tosoh Corporation) and bis (dimethylaminoethyl), which are generally used as a catalyst for the production of polyurethane resins, are used. ) When an ether 70% dipropylene glycol solution (TOYOCAT-ET, manufactured by Tosoh Corporation) is used (Comparative Example 4 to Comparative Example 6), the odor of the amine catalyst is confirmed from the foam, and the vehicle instrument is attributed to the amine catalyst. It is impossible to prevent PVC discoloration of the panel and fogging of the window glass.

Claims (5)

The following general formula (1)

[Wherein, X represents a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group. ]
1 or 2 selected from the group consisting of an amine compound represented by the formula: triethanolamine, bisdimethylaminoethyl ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, and hexamethyltriethylenetetramine A catalyst composition for producing a polyurethane resin comprising at least a tertiary amine compound. The catalyst composition for producing a polyurethane resin according to claim 1, wherein the amine compound represented by the general formula (1) is 2-hydroxymethyltriethylenediamine. The mixing ratio of the amine compound represented by the general formula (1) and the tertiary amine compound is [amine compound represented by the general formula (1)] / [tertiary amine compound] = 1/30 to 30 / The catalyst composition for producing a polyurethane resin according to claim 1 or 2, wherein the catalyst composition is 1 (weight ratio). A process for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition according to any one of claims 1 to 3. The usage-amount of the catalyst composition in any one of Claim 1 thru | or 3 is the range of 0.01-30 weight part with respect to 100 weight part of polyols, The Claim 4 characterized by the above-mentioned. A method for producing a polyurethane resin.