JP2003081975A - New amidine compound, method for manufacturing the same and usage of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amidine compound having no trouble of bleeding out from the polyurethane resin and useful as a reaction catalyst for an isocyanate compound. SOLUTION: The amidine compound expressed by general formula [I] (wherein, R<1> is H or a 1-3C alkyl; R<2> is H, a 1-16C alkyl or alkylene, or phenyl; R<1> and R<2> together may form a 5-8C ring; R<3> is H or a 1-3C alkyl; and m is an integer of 2-4) is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amidine compound, and more particularly to a novel amidine compound useful as a reaction catalyst for isocyanate compounds, a method for producing the same, and a method for using the same.

[0002]

2. Description of the Related Art Conventionally, as amidine compounds, 1,8
-Diazabicyclo [5.4.0] -7-undecene,
1,5-diazabicyclo [4.4.0] -5-decene,
Alternatively, 1,5-diazabicyclo [4.3.0] -5-
Nonen is known. These amidine compounds are organic compounds having a very strong basicity, and are used in the form as they are or in the form of salts with various organic acids and inorganic acids, and further in the form of quaternary ammonium salts, in the production of polyurethane resins. It is used as a reaction catalyst for compounds, a curing accelerator for epoxy resins, and a dehydrohalogenating agent for alkyl halides in olefin synthesis.

[0003]

However, since conventional amidine compounds and salts thereof do not have a functional group that reacts with an isocyanate group, these amidine compounds are used as reaction catalysts for polyols and isocyanate compounds in the production of polyurethane resins. When used, there was a problem that the above-mentioned amidine compound gradually bleeded out on the surface of the polyurethane resin with the passage of time. For example, in a polyurethane cushion obtained by laminating polyvinyl chloride on polyurethane foam, a phenomenon in which the bleed-out amidine compound reacts with the polyvinyl chloride of the cushion skin to gradually discolor the surface, a so-called vinyl stain phenomenon There was a problem that occurred. Therefore, it is an object of the present invention to provide an amidine compound that does not bleed out from a polyurethane resin and is useful as a reaction catalyst for an isocyanate compound.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when a new amidine compound having a hydroxyl group is used, the amidine compound is originally used in the production of polyurethane resin. The present invention has been completed by finding that the problem of bleed-out can be solved without impairing the catalytic effect of the isocyanate compound of 1. That is, the present invention is
It is an amidine compound represented by the general formula [I].

[Chemical 3] (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom, an alkyl group or an alkylene group of 1 to 16 carbon atoms or a phenyl group. Further, R ¹
And R ² may combine with each other to form a ring having 5 to 8 carbon atoms. R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m shows the integer of 2-4. )

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As described above, the amidine compound of the present invention is represented by the general formula [I], and in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include, for example, methyl group, ethyl group, n
A propyl group and the like. R ² represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms or an alkylene group, or a phenyl group. Examples of the alkyl group or alkylene group having 1 to 16 carbon atoms include saturated alkyl groups such as methyl group, ethyl group, hexyl group and stearyl group; alkylene groups such as 3-butylene group and 7-octylene group; butoxymethyl group. And substituted alkyl groups such as phenoxymethyl group, methacryloyloxymethyl group, benzoyloxymethyl group, fluoromethyl group and chloromethyl group. When R ² is a phenyl group, the phenyl group may be substituted with a halogen group, an alkyl group, a substituted alkyl group or the like, and examples thereof include a fluoro group, a methyl group,
4-chloromethyl phenyl group etc. are mentioned.

In addition to the above-mentioned ones, R ¹ and R ² may be bonded to each other to form a ring having 5 to 8 carbon atoms. Examples of the ring having 5 to 8 carbon atoms formed by R ¹ and R ² bonded to each other include a cyclopentane ring, a cyclohexane ring, a norbornane ring,
A cyclooctane ring etc. are mentioned. These rings may have various substituents, and examples of the substituents include a methyl group, a vinyl group and a 1-methylvinyl group.

R ³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group having 1 to ³ carbon atoms of R ³ include a methyl group, an ethyl group and an n-propyl group.

Of the R ¹ , R ² and R ³ mentioned above, R ¹ , R ² and R ³ are all hydrogen atoms in view of the ease of distillation and purification during the production of the amidine compound of the present invention. Or R ¹ ,
It is preferred that R ³ is a hydrogen atom and R ² is a methyl group.
In the above formula, m is an integer of 2 to 4, but 2 or 4 is preferable for the same reason. That is, as a preferred specific example of the novel amidine compound of the present invention, 6- (2-
Hydroxyethyl) -1,8-diazabicyclo [5.
4.0] -7-Undecene, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] -7-
Undecene, 7- (2-hydroxyethyl) -1,5-
Diazabicyclo [4.3.0] -5-nonene, 7- (2
-Hydroxypropyl) -1,5-diazabicyclo [4.3.0] -5-nonene.

The amidine compound of the present invention can be produced according to the following reaction formula.

[0010]

[Chemical 4]

That is, after the amidine compound represented by the general formula [II] is anionized with an anionizing agent, a monoepoxy compound is added thereto and then treated with a proton donating compound (proton source) to give a hydroxyl group. It is possible to obtain a novel amidine compound of the present invention having

As the amidine compound represented by the general formula [II], 1,8-diazabicyclo [5.4.0] -7-
Undecene, 1,5-diazabicyclo [4.4.0]-
5-decene, 1,5-diazabicyclo [4.3.0]-
Examples include 5-nonene. The reaction for anionizing the amidine compound represented by the general formula [II] with an anionizing agent is preferably carried out in a solvent in order to easily control the heat of reaction and to avoid solidification of the generated anion. . The solvent does not react with an anionizing agent, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane; aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; Alternatively, a mixture thereof may be used.

As the above-mentioned anionizing agent, known ones can be used, for example, organic metal compounds such as n-butyllithium and methylmagnesium bromide; inorganic hydrides such as lithium hydride, sodium hydride and lithium aluminum tetrahydride. Compounds: alkoxides such as potassium-t-butoxide and the like can be mentioned. It is convenient and preferable to use these anionizing agents as a solution of the above ethers, aliphatic or aromatic hydrocarbons. The amount of the anionizing agent used is usually 0.9 to 2.0 mol, preferably 1.0 to 1.1 mol, per 1 mol of the amidine compound represented by the general formula [II]. The anionization reaction of the amidine compound represented by the general formula [II] is carried out by adding a solution of the anionizing agent dropwise to the solution of the amidine compound at a temperature of −78 to 100 ° C., preferably 50 to 40 ° C. 0.5 ~ at temperature
It is completed by stirring for 5 hours.

In the method for producing an amidine compound of the present invention, a monoepoxy compound is subjected to ring-opening addition to the anionized amidine compound represented by the general formula [II] after the anionization reaction. As the monoepoxy compound, as shown in [Chemical Formula 4], ethylene oxide described above R ¹
Those substituted with R ² and R ³ , for example, ethylene oxide, propylene oxide, 1,2-butene oxide, 2,3-pentene oxide, α-C6-18
Alkylene oxides such as olefin oxide, styrene oxide and 4-chloromethylstyrene oxide; cyclopentene oxide, cyclohexene oxide, 4-vinyl-1-cyclohexene oxide,
Alicyclic epoxides such as limonene-1,2-oxide, isophorone oxide, 2,3-epoxynorbornene, and cyclooctene oxide; butyl glycidyl ether, heptyl glycidyl ether, higher alcohol (C10-16) glycidyl ether, Allyl glycidyl ether, phenyl glycidyl ether, 4-
Glycidyl ethers such as methoxyphenyl glycidyl ether; and glycidyl esters such as glycidyl butyrate, glycidyl methacrylate, and glycidyl benzoate. Among these monoepoxy compounds, a low molecular weight monoepoxy compound is preferable, and ethylene oxide and propylene oxide are particularly preferable, from the viewpoint of easy distillation and purification of the obtained amidine compound.
Incidentally, these epoxy compounds may be used alone,
You may use 2 or more types together if needed. The amount of the monoepoxy compound used is usually 0.9 to 2.0 mol, preferably 1.0 to 1.1 mol, per 1 mol of the anionizing agent used.

The ring-opening addition of the monoepoxy compound is carried out by dropping the monoepoxy compound at -78 to 50 ° C, preferably -50 to 30 ° C, into the anionized amidine compound represented by the general formula [II]. Then, the mixture is stirred at the same temperature for 1 to 3 hours, and if necessary, at 30 to 80 ° C. for 1 to 3 hours. The monoepoxy compound may be dropped as it is, or may be dropped as a solution of the ethers or hydrocarbons described above.

After the ring-opening addition of the above monoepoxy compound, it is carried out at 0 to 50 ° C., preferably 10 to 30 ° C., usually 1.0 to 5.0 mol, preferably 1 mol to the anionizing agent used.
Add 1.5 to 2.0 mol of the proton donating compound (proton source) and stir for 1 to 3 hours. Examples of the proton source include water, methanol, ethanol, isopropanol and the like. After adding the above-mentioned proton source and removing metal hydroxide or metal alkoxide that precipitates when stirred for 1 to 3 hours by filtration or centrifugation, unreacted raw material amidine compound, proton source and solvent are distilled off. As a result, the novel amidine compound of the present invention represented by the general formula [I] is obtained. The obtained amidine compound can be used for various purposes as it is, but when higher purity is required, it is purified by vacuum distillation and used. The novel amidine compound of the present invention can be used as it is or in the form of a salt of an organic acid or an inorganic acid, or in the form of a quaternary ammonium salt, as a reaction catalyst for an isocyanate compound.

Examples of the organic acid or inorganic acid used for producing the salt of the amidine compound of the present invention include saturated fatty acids such as acetic acid, propionic acid, caproic acid, 2-ethylhexanoic acid, lauric acid and stearic acid. Unsaturated fatty acids such as acrylic acid, crotonic acid, oleic acid, linoleic acid; lactic acid, glycolic acid, ricinoleic acid,
Oxy fatty acids such as hydroxystearic acid; dibasic fatty acids such as succinic acid and adipic acid; aromatic carboxylic acids such as benzoic acid, salicylic acid, phthalic acid and terephthalic acid; phenols such as phenol, cresol, resorcinol, catemar and phenol novolac resin Kind;
Examples thereof include organic phosphoric acid esters such as dibutyl phosphate and monolauryl phosphate; sulfuric acid esters and sulfonic acids such as lauryl sulfate and dodecylbenzenesulfonic acid; and inorganic acids such as carbonic acid, boric acid, sulfuric acid, phosphoric acid and hydrochloric acid.

Since the reaction for synthesizing the organic acid or the inorganic acid salt of the amidine compound of the present invention generates heat by the neutralization reaction,
Normally 1.0 to 1 mol with respect to 1.0 mol of the liquid amidine compound.
It is preferable to gradually add 1 mol, preferably 1.0 mol of acid under cooling. If the salt obtained is a solid, it is reacted at a temperature above the melting point, the product is taken out in the molten state, solidified and then ground, or neutralized in an ether solvent, a ketone solvent, or a hydrocarbon solvent. The reaction may be carried out, and the precipitated salt may be filtered, collected and dried.

The quaternary salt of the amidine compound of the present invention is a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate in the absence of a solvent or in the presence of an alcohol, an ester or a ketone as a solvent; methyl chloride, butyl bromide or chloride. It can be obtained by reacting an alkyl halide such as benzyl; or a dialkyl sulfuric acid such as dimethyl sulfuric acid or diethyl sulfuric acid with an amidine compound. Further, the quaternary salt of the amidine compound of the present invention in which the counter ion is a residue of the above-mentioned phenols or carboxylic acids is, for example, phenols or carboxylic acids added to the alkyl carbonate obtained by the above reaction. Then, the solvent can be easily distilled off by heating.

The novel amidine compound of the present invention, particularly the salt thereof, can be used as a reaction catalyst for isocyanate compounds. Here, the reaction of an isocyanate compound refers to a reaction of forming a polyurethane resin with a polyol, a reaction of forming a uretidione or isocyanurate compound by dimerization or trimerization of an isocyanate compound, and a reaction of forming a carbodiimide by decarboxylation of 2 moles of an isocyanate compound. .

The above-mentioned isocyanate compound and polyol are raw materials ordinarily used for producing rigid, semi-rigid, flexible polyurethane foams, elastomer foams, polyurethane molded products and the like, and are not particularly limited. Specific examples of the above-mentioned isocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate; alicyclic isocyanates such as hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate; modification thereof. And a prepolymer containing a terminal isocyanate group by the reaction of these with a polyol.

Specific examples of the above-mentioned polyols include polymer polyols such as alkylene oxides such as ethylene oxide, propylene oxide, 1,2- and 1,4-butylene oxide, glycols such as ethylene glycol and propylene glycol; Glycerin, trimethylolpropane, triethanolamine,
Polyhydric alcohols such as pentaerythritol, sorbitol, sucrose and other polyols having three or more hydroxyl groups, ethylenediamine, diethyltriamine, tolylenediamine, xylylenediamine, piperazine, N
-Aminoalkylpiperazine, N, N-dimethylaminopropylamine, a polyether polyol obtained by addition polymerization using an amine compound such as cyclohexylenediamine as an initiator; acrylonitrile, styrene, methyl methacrylate in the polyether polyol, Polymer polyols obtained by radically polymerizing ethylenically unsaturated monomers such as butadiene; polycarboxylic acids such as succinic acid, sebacic acid, maleic acid, adipic acid, fumaric acid, phthalic acid and dimer acid, and the above polyhydric alcohols. And a polyester polyol obtained by a reaction with a polycarboxylic acid and a polyether; and a mixture of two or more thereof.

In the reaction of the above isocyanate compound, an active hydrogen compound as a crosslinking agent or a chain extender can be used if necessary. Examples of such active hydrogen compounds include triethanolamine, diethanolamine, ethylene glycol, diethylene glycol, butanediol, trimethylolpropane,
Low molecular weight polyols such as glycerin and p-bis (2-hydroxyethyl) phenylene ether, tolylenediamine, xylylenediamine, diaminodiphenylmethane,
Mention may be made of polyamines such as methylenebis-o-chloroaniline.

In the reaction of the above isocyanate compound, other additives can be used if necessary. For example, fluorine-based hydrocarbons, halogen-substituted hydrocarbon-based foaming agents such as methylene chloride, carbon dioxide, foaming agents such as water, surfactants such as silicone foaming agents, colorants, fillers, flame retardants, stabilizers, etc. Is mentioned. Further, the amidine compound of the present invention and its salt can be used in combination with other known urethane catalysts, and the total amount thereof is usually 0.01 to 5 parts by weight, preferably 100 parts by weight of the polyol. 0.1 to 2 parts by weight. If the total amount of the amidine compound of the present invention and its salt and other urethane catalysts is less than 0.01 parts by weight, the catalytic activity is low, and it takes too long to complete the reaction, and if it is more than 5 parts by weight, the pot life becomes short, Workability deteriorates.

[0025]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the following, parts and% indicate parts by weight and% by mass, respectively. In addition, in Tables 1 to 3, DBU; 1,8-diazabicyclo [5.4.
0] -7-undecene, DBN; 1,5-diazabicyclo [4.3.0] -5-nonene, HE-DBU; 6-
(2-Hydroxyethyl) -1,8-diazabicyclo [5.4.0] -7-undecene, HP-DBU; 6-
(2-Hydroxypropyl) -1,8-diazabicyclo [5.4.0] -7-undecene, HP-DBN; 7-
(2-Hydroxypropyl) -1,5-diazabicyclo [4.3.0] -5-nonene, HE-DBN; 7- (2
-Hydroxyethyl) -1,5-diazabicyclo [4.
3.0] -5-nonene.

Example 1 Synthesis of 6- (2-hydroxyethyl) -1,8-diazabicyclo [5.4.0] -7-undecene (HE-DBU): 1,8-diazabicyclo [5.4] 0.0] -7-Undecene (DBU) (152 g, 1 mol) was added to tetrahydrofuran (900 g), and the temperature was set to -20 ° C in a dry ice / acetone bath.
Cooled to. To this, 437 g of 14.7% hexane solution of n-butyllithium (64 g of pure content, 1.05 mol) was added at a liquid temperature of -10 ° C or lower
It was added dropwise in 3 hours. Then, after stirring at the same temperature for 1 hour, 0
47.9 g (1.09 mol) of ethylene oxide was passed in at a temperature not exceeding ° C in 3 hours. And at the same temperature for 1 hour,
After stirring at 20 ° C. for 1 hour, 18.9 g (1.05 mol) of water was added, the mixture was stirred at room temperature for 1 hour, and the precipitated inorganic substances were removed by filtration. After removing the solvent from the filtrate at atmospheric pressure, unreacted DBU was distilled off under reduced pressure to obtain 86 g (yield 44%) of HE-
I got DBU. Various analytical values of the obtained HE-DBU are shown below. The unit of amine value is mgKOH / g. (Analysis) total amine value (HClO ₄ Method) 283 (theoretical 28
6) Tertiary amine value (HCl method) 263 (theoretical value 286). Purity 92.9% by gas chromatography (hydrolysis of C = N double bond of HE-DBU was detected as an impurity peak).

(Example 2) 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] -7-undecene (HP-DBU)
Synthesis: In the same manner as in Example 1 except that 60.9 g (1.05 mol) of propylene oxide was added dropwise instead of ethylene oxide, 136.5 g (yield 65%) of HP-DBU was obtained. Various analytical values of the obtained HP-DBU are shown below. The unit of amine value is mgKOH / g. (Analysis) total amine value (HClO ₄ Method) 269 (theoretical 26
7) Tertiary amine value (HCl method) 256 (theoretical value 267). Purity 95.9% by gas chromatography. This product was further purified by distillation under reduced pressure, boiling point 160 ° C / 1 mmHg, 116 g HP
-I have a DBU product. The various analytical values of this HP-DBU product are shown below. (Analysis) total amine value (HClO ₄ Method) 267 (theoretical 26
7) Tertiary amine value (HCI method) 263 (theoretical value 267). Purity 99.0% by gas chromatography.

Example 3 Synthesis of 7- (2-hydroxypropyl) -1,5-diazabicyclo [4.3.0] -5-nonene (HP-DBN): 1,5-diazabicyclo [4.3] .0] -5-nonene (DBN) 124 g (1 mol) in diethyl ether 700 g
In addition, the mixture was cooled to 10 ° C or lower in an ice bath. 350g of 3.0M diethyl ether solution of methylmagnesium bromide
(Purity of 125.2 g, 1.05 mol) was added dropwise at 10 to 20 ° C. for 2.5 hours. After stirring at 20 to 30 ° C. for 2 hours, 60.9 g (1.05 mol) of propylene oxide was added dropwise over 2 hours, and the mixture was further stirred at the same temperature for 2 hours. Then, 64 g (2 mol) of methanol was added at room temperature, the mixture was stirred for 3 hours, and then the reaction solution was allowed to stand to precipitate an inorganic substance. The solvent is distilled off from the supernatant liquid under atmospheric pressure, and the residue is purified by vacuum distillation to give a boiling point of 148 ° C / 1 mmHg, 131
g (yield 72%) of HP-DBN was obtained. The obtained HP-
Various analysis values of DBN are shown below. The unit of amine value is mgKOH / g. (Analysis) total amine value (HClO ₄ Method) 308 (theoretical 30
8) Tertiary amine value (HCI method) 304 (theoretical value 308). Purity 98.5% by gas chromatography.

Example 4 Synthesis of 7- (2-hydroxyethyl) -1,5-diazabicyclo [4.3.0] -5-nonene (HE-DBN): 47.9 g (instead of propylene oxide) Example 3 except that 1.09 mol of ethylene oxide was added dropwise.
In the same manner as described above, 84.0 g (yield 50%) of HE-DBN was obtained. Various analytical values of the obtained HE-DBN are shown below.
The unit of amine value is mgKOH / g. (Analysis) total amine value (HClO ₄ Method) 336 (theoretical 33
4) Tertiary amine value (HCI method) 322 (theoretical value 334). 92.0% purity by gas chromatography. This product was further purified by vacuum distillation, boiling point 130 ° C / 1mmHg, 75g HE
-A DBN product is obtained. The various analytical values of this HE-DBN product are shown below. (Analysis) total amine value (HClO ₄ Method) 334 (theoretical 33
4) Tertiary amine value (HCI method) 330 (theoretical value 334). Purity 99.0% by gas chromatography.

Example 5 Synthesis of Carboxylic Acid Salt of Novel Amidine Compound: 10.5 g (0.054 mol) of HE-DBU obtained in Example 1 was mixed with 7.8 g (0.054 mol) of 2-ethyl at room temperature under nitrogen atmosphere. Hexanoic acid was added, and the mixture was stirred for 1 hour. HE-DB with a light brown color and high viscosity
U of 2-ethylhexanoate was obtained. Similarly, HP-DBU, HP-DBN, HE obtained in Examples 2, 3, and 4 were used.
-DBN 2-ethylhexanoate was obtained. Table 1 shows these various analysis values. In Table 1, the unit of total amine value is mgKOH / g, and the IR absorption is a thin film (NaC
l), C = O absorption (cm ^-1 ).

[0031]

[Table 1]

Example 6 Effect as Reaction Catalyst for Polyurethane Foam: Polyol; Sannix FA-703 (manufactured by Sanyo Chemical Industry Co., Ltd.,
Trade name), isocyanate compound; Crude MDI (C
RMDI, manufactured by Sumitomo Bayer Co., Ltd., index 105, trade name), water, and a raw material (raw material temperature 25 ° C.) formulated with 2-ethylhexanoate of an amidine compound as a reaction catalyst at a mixing ratio shown in Table 2 is used as a release agent. As bond wax UR
Mold with T-35T (Bond Wax KK., Trade name) applied to the inner surface (size 20 cm x 20 cm x 1 cm, mold temperature 40)
C.) and foamed and cured under curing conditions for 10 minutes at room temperature to obtain a polyurethane rigid foam. Then
40 g of the obtained polyurethane rigid foam was cut into pieces of about 5 mm square with scissors, added to 1,000 g of methanol, and stirred under heating under reflux for 48 hours. After cooling to room temperature, the polyurethane rigid foam was removed by filtration, and the methanol in the filtrate was distilled off under normal pressure. Then, the amount of the extracted reaction catalyst was measured from the total amine value of the residual liquid, and the extraction rate (%) of the reaction catalyst was obtained. The results are shown in Table 2.

[0033]

[Table 2]

From the results shown in Table 2, the extraction ratio of the amidine compound of the present invention having a hydroxyl group from the polyurethane rigid foam is considerably lower than that of the conventional DBU and DBN, which indicates that the amidine compound of the present invention is It has been found to be useful as a reaction catalyst for polyurethane foam.

(Example 7) Production example of PVC sheet laminated polyurethane foam and discoloration degree of PVC sheet: polyol; Sannix F
A-703 (same as above), 100 parts by weight of triethanolamine, 4 parts by weight of water, 2.5 parts by weight of water, and 1.0 part by weight of 2-ethylhexanoate of amidine compound as a reaction catalyst were uniformly mixed, and mixed with crude MDI (same as above). ) 58.9 parts by weight was added and stirred for 7 seconds with a high-speed stirrer. Then, a bond wax URT-35T (same as above) was applied to the inner surface as a release agent, and a light brown slush molded PVC sheet of 10 cm × 10 cm was previously attached to the inner surface with a double-sided adhesive tape (size 20 cm × 20 cm × 1cm, mold temperature 40 ℃), inject the obtained raw material (raw material temperature 25 ℃), foam and cure under curing condition at room temperature for 10 minutes, and density of each catalyst (excluding PVC) 0.13 to 0.14 A good PVC sheet-laminated polyurethane foam with g / cm ³ was obtained. Then, these PVC sheet laminated polyurethane foams were placed in a constant temperature dryer at 120 ° C., and the discoloration state of the PVC sheet when continuously heated was examined. The results are shown in Table 3. In Table 3, ∘ means no discoloration, Δ means discoloration around the vinyl chloride sheet to black brown, and x means discoloration on the entire vinyl chloride sheet to black brown.

[0036]

[Table 3]

As can be seen from the results in Table 3, when the amidine compound of the present invention was used, discoloration of the vinyl chloride sheet due to the bleed-out of the amidine compound was not observed at all, unlike the conventional amidine compounds.

[0038]

INDUSTRIAL APPLICABILITY The novel amidine compound of the present invention has an effect equivalent to that of a conventional amidine compound as a reaction catalyst for an isocyanate compound, and further, a hydroxyl group in the molecule reacts with an isocyanate group to form a conventional amidine compound. The vinyl stain problem in vinyl chloride laminated polyurethane foam, which cannot be avoided by the compound, can be significantly improved. Thus, the novel amidine compound of the present invention does not bleed out and is extremely useful as a reaction catalyst for isocyanate compounds in the production of polyurethane resins and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Michiharu Okubo             11 Ichibashi-nohonmachi, Higashiyama-ku, Kyoto-shi, Kyoto             Napuro Co., Ltd. F-term (reference) 4C050 AA01 BB08 CC10 EE02 FF02                       GG01 HH01                 4C065 AA03 BB10 CC01 DD02 EE02                       HH04 JJ01 KK01 LL01 PP01                       QQ04                 4G069 AA02 AA08 BA21A BA21B                       BA21C BA36C BE20A BE20B                       BE20C BE38A BE38B BE38C                       CB25 CB46 CB72 FA01 FC04                 4J034 CA01 CA02 CA04 CA05 CA12                       CA13 CB02 CB03 CB04 CC12                       CC22 CC26 CC45 CC52 CC61                       CC62 CC65 CC67 CD04 CD13                       DA01 DB04 DB05 DC50 DF01                       DF16 DF20 DF21 DF22 DF27                       DG03 DG04 DG05 DG08 DG14                       DG23 DQ05 DQ09 DQ15 DQ16                       DQ18 HA01 HA07 HC03 HC12                       HC17 HC22 HC46 HC52 HC61                       HC63 HC67 HC71 HC73 KA01                       KB02 KB03 KB04 KD11 KE02

Claims (4)

[Claims] 1. An amidine compound represented by the general formula [I]. [Chemical 1] (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom, an alkyl group or an alkylene group of 1 to 16 carbon atoms or a phenyl group. Further, R ¹
And R ² may combine with each other to form a ring having 5 to 8 carbon atoms. R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m shows the integer of 2-4. ) 2. The amidine compound according to claim ¹ , wherein in the general formula [I], R ¹ and R ³ are hydrogen atoms, R ² is a hydrogen atom or a methyl group, and m is 2 or 4. 3. An amidine compound represented by the general formula [II] is anionized with an anionizing agent, a monoepoxy compound is added thereto, and then the compound is treated with a proton donating compound. ] The manufacturing method of the amidine compound shown by these. [Chemical 2] (In the formula, m represents an integer of 2 to 4.) 4. An isocyanate compound represented by the general formula [I]
A method for using an amidine compound, which comprises reacting by using the amidine compound or a salt thereof as a catalyst.