JPS62138518A - Production of highly elastic urethane foam - Google Patents

Abstract

PURPOSE:To obtain the titled urethane foam having high hardness and removable from a mold in a short time, in high productivity, by reacting an organic polyisocyanate with a polyol, etc., in the presence of an amine catalyst of a specific structural formula and a crosslinking agent. CONSTITUTION:The objective urethane foam can be produced by reacting (A) an organic polyisocyanate with (B) a polyol and (C) a crosslinking agent [containing a primary amine of formula I (R is alkyl) and/or its derivative as at least a part thereof] in the presence of (D) a foaming agent, (E) a catalyst [containing an amine catalyst of formula II (R1 and R2 are alkyl) as at least a part thereof] and, if necessary, (F) other adjuvants. Preferably, the compound of formula II is the one having >=2C alkyl as R1, especially 1,3,5-tris(3- dimethylamino-propyl)-hexahydro-S-triazine and the derivative of the primary amine is salt or amide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a highly elastic urethane foam (hereinafter abbreviated as HR foam).

[Conventional technology]

As a conventional method for producing HR foam, there is a method using 2-a, minnow-2-ethyl-1,3-propanediol and an amine catalyst such as triethylenediamine (for example, JP-A-53-16097).

[The flood point that the invention is trying to solve]

However, this material is soft and hard to get hard. In addition, there are problems such as demolding in a short time and poor productivity, making it impractical.

Means for Solving the Problems] The present inventors have conducted intensive studies to obtain a straight elastic urethane foam that is hard and can be demolded in a short period of time, and as a result, has arrived at the present invention. That is, the present invention provides a method for producing a urethane foam by reacting an organic polyisocyanate, a polyol, and a reticulating agent in the presence of a blowing agent, a catalyst, and, if necessary, an auxiliary agent thereof, in which, as part of the catalyst, Using an amine catalyst represented by the general formula (in which R, R2 represents an alkyl group), as at least a part of the reticulating agent,
This is a method for producing a highly elastic urethane foam characterized by using a primary amine represented by the general formula % (2) (wherein R represents an alkyl group) and/or a derivative thereof.

- In general formula (1), the number of carbon atoms in the alkyl group of R, and R2 is preferably 2 to 3. R2 is 1-2.

Specific examples of the compound represented by general formula (1) include 1,
8.5-Tris(3-dimethylamino-propyl)-hexahydro-5-)riazine, 1,8.5-1-lis(
3-diethylamino-propyl)-hexahydro-6-
Triazine, 1,3.5-tris(3-dimethylamino-ethyl)-hexahydro-5-triazine, 1.3
．． 5 = tris(3-diethylamino-ethyl)-hexahydro-5-1 riazine, and the like.

In the present invention, the amine catalyst represented by general formula (1) can be used in combination with other catalysts as follows, if necessary. Other tertiary amine catalysts such as trimethylamine, triethylamine, dimethylpiperazine,
N-ethylmorpholine, N-methylmorpholine, dimethylethanolamine/diethylethanolamine, N,
N-dimethylcyclohexylamine, dimethylbenzylamine/triethylenediamine and their formates, dimethylaniline, l,2-dimethylimidazole, pyridine, quinoline, DBU C San Abbott Co., Ltd.] and their organic acid salts (oleate, ferulate) etc.), organometallic catalysts such as tin catalysts (dibutyltin dilaurate, stannous octoate, tin maleate catalysts, tin mercaptide, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, etc.), mercury acetate. , cobalt naphthenate, etc., and carboxylic acid alkali metal salt catalysts such as potassium octylate, potassium acetate, and the like. Among these, preferred are tertiary amine catalysts.

The content of the amine catalyst represented by the general formula (1) is usually 100 to 100% based on the total weight of the amine catalyst and other catalysts.
5%, preferably ioo to 25%.

+ & In formula (2), the alkyl group for R is usually an alkyl group having 1 to 4 carbon atoms (methyl, ethyl).

propyl, butyl, etc.), preferably ethyl.

Specific examples of the primary amine represented by general formula (2) include 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and 2-amino-2-ethyl-1,3-propanediol. Examples include amino-2-propyl-1,3-propanediol and 2-amino-2-butyl-1,3-propanediol.

Examples of derivatives of the 91st class amine include salts and amides of the above amines. Acids used to form salts include: carboxylic acids (aliphatic carboxylic acids such as oleic acid and octylic dioxycarboxylic acid), sulfonic acids (alkanesulfonic acids, toluenesulfonic acids, etc.)
, phenols, etc.], none←′! 1 acid [phosphoric acid, carbonic acid,
Boric acid, etc.] can be used. Specific examples of these acids include JP-A No. 55-9871, JP-A No. 46-1
Publication No. 0549.

and acids used for salt formation with amines as described in Japanese Patent Publication No. 46-2672.

Among the acids, preferred are organic acids, and more preferred are carboxylic acids (especially oleic acid and octylic acid).

Amides include carbonamides and sulfonamides (
(amides with the above carboxylic acids or sulfonic acids).

Two or more types of primary amines and their derivatives may be used in combination, and mixtures of amines and derivatives (salts and/or amides) [the amine is partially replaced by a fatty acid (for example, the primary
It is also possible to use a reaction mixture in which 30 to 60% of the primary amino groups are neutralized and/or amidated.

Among the primary amines and derivatives thereof, preferred are:
2-amino-2-methyl-1,3-propanediol,
2-ethyl-1,3-propanediol,
2-amino-2-propyl-1°3-propanediol, 2-amino-2-butyl-1,3-propanediol, salts of these amines with fatty acids such as oleic acid (amine soaps) and/or amides ; and mixtures thereof (mixtures of amides and/or amine soaps obtained by the reaction of the above-mentioned amines and fatty acids with active amines), and particularly preferred are 2-amino-2
-ethyl-1,3-propanediol.

In the present invention, in addition to the primary amine represented by general formula (2) and/or its derivative, other reticulating agents may be used in combination as necessary. Such reticulating agents include active hydrogen-containing groups (OH.

Examples include low-molecular compounds having at least two molecules (NH2, NH, etc.), such as polyols, polyamines, and amino alcohols. The polyols include polyhydric alcohols, which will be described later as raw materials for polyether polyols,
Examples include low molar AO adducts of polyfunctional compounds containing active hydrogen atoms, such as polyhydric phenols, polycarboxylic acids, and amine compounds. Examples of polyamines include aliphatic, alicyclic/aromatic, and heterocyclic polyamines. Amino alcohols include ethanolamine and propatoolamine.

Examples include oxydianiline. The molecular weight (molecular weight per active hydrogen atom-containing group) of these reticulating agents is usually 30
-200, preferably 30-150. The number of functional groups is usually 2 to 8, preferably 3 to 6.

The content of the primary amine and/or its derivative represented by general formula (2) is usually 10
It is 0-30%, preferably 100-50%.

Examples of the polyol in the present invention include polymer polyols such as polyether polyols, polyester polyols, polyether ester polyols and polymer polyols, and combinations of two or more of these.

Polyether polyols include polyhydric alcohols and polyether polyols.
Compounds with structures in which alkylene oxide is added to active hydrogen atom-containing polyfunctional compounds such as convex phenols, polycarboxylic acids, and aminated adducts are mentioned.

Examples of the polyhydric alcohols include glycols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, etc.); triols (glycerin, trimethylolpropane, etc.); Alcohols (pentaerythritol, diglycerin, sorbitol, sho, etc.); Polyhydric phenols include polyhydric alcohols (pyrogallol, hydroquinone, etc.), bisphenols (bisphenol A, etc.), novolak resins having two or more phenolic hydroxyl groups, resols Resin intermediates, etc. Polycarboxylic acids include aliphatic polycarboxylic acids (succinic acid, adipic acid, etc.), aromatic polycarboxylic acids (phthalic acid, etc.).

terephthalic acid, trimellitic acid, etc.). Examples of amine compounds include monoamines (ammonia, butylamine, etc.), aliphatic polyamines (ethylenediamine, hexamethylene diamine, diethylene triamine, etc.), monocyclic polyamines (cyclohexylene diamine, isophorone diamine, etc.), and aromatic polyamines (phenylene diamine, etc.). , tolylene diamine, xylene diamine, diphenylmethanediamine/polyphenylmethane polyamine, etc.), polycyclic polyamines (piperazine, N-aminoethylpiperazine, etc.), alkanolamines (monoethanolamine, jetanolamine, triethanolamine, [such as triisopropanolamine].

Preferred among these are polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, and amine compounds such as ethylenediamine and triethanolamine. Two or more kinds of active water atom-containing compounds can also be used.

The alkylene oxide (hereinafter abbreviated as AO) added to the above-mentioned active water atom-containing compound is ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO).
), butylene oxide.

Examples include tetrahydrofuran, styrene oxide, and epichlorohydrin.

AO may be used alone or in combination of two or more. In the case of head throwing, block addition, random addition, or a mixture of both may be used, but block addition (chipped type) is acceptable.

Balanced type) is preferred.

Among these AOs, PO and/or EO are preferable, but other AOs may be used depending on the required performance.
It is also preferable to use a small amount of O (butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, etc.). From the viewpoint of reactivity, a combination system of PO and EO (usually 70:80-95: by weight ratio) is preferable.
5, especially so: 20-90: 10).

Addition of AO can be carried out in a conventional manner, without a catalyst,
Or catalyst (alkali catalyst, amine catalyst.

(especially in the latter stages of alkylene oxide addition) under normal or elevated pressure.

Examples of polyester polyols or polyether ester polyols include polymerized polyester polyols obtained by reacting low-molecular-weight polyols (or polyether polyols) with dicarboxylic acids (or dicarboxylic acid anhydrides and AO), and ring-opening polymerization of lactones. Examples include polyester polyols. Examples of the low-molecular polyols include diols such as ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, and bis(hydroxyethyl)benzene; trimethylolpropane, glycerin, etc. A mixture thereof is mentioned. Examples of dicarboxylic acids include succinic acid, glutaric acid, adipic acid/sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, dimer acid, and mixtures thereof. Examples of the lactone include ε-caprolactone.

? As the combined polyol, the above polyol (polyether polyol and/or polyester polyol)
and polymerization can 4 polyols derived from ethylenically unsaturated monomers. Examples of monomers include (a) (meth)acrylic acid (referring to acrylic acid and methacrylic acid; the same expressions will be used hereinafter) and its derivatives (tolyl, esters, salts, amides, etc.), such as (meth)acrylonitrile;

Methyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylamide; (b) Aromatic vinyl monomers such as styrene, α-methylstyrene; (C)
Olefinic hydrocarbon monomers such as ethylene, propylene, butadiene, isobutylene, isoprene, 1.4
-Pentadiene; (C1) Vinyl ester monomers such as vinyl acetate; (e) Vinyl halide monomers such as vinyl chloride and vinylidene chloride; (f) Vinyl ether monomers such as vinyl methyl ether. Among these, preferred are acrylonitrile, methyl methacrylate, styrene, and butadiene.

Particularly preferred are acrylonitrile and a combination of acrylonitrile and styrene (styrene:acrylonitrile weight ratio of 0:100 to 60:40). The proportions of polyol and monomer used in the polymer polyol can vary over a wide range.

Usually 2 to 70 parts by weight, preferably 5 parts by weight of ethylenically unsaturated monomer (or polymer) per 100 parts by weight of polyol.
~4oM parts. A polymer polyol can be produced from a polyol and an ethylenically unsaturated single W compound by a conventional method. For example, a method in which an ethylenically unsaturated single F compound is polymerized in a polyol in the presence of a polymerization catalyst (radical generator, etc.) or a method in which a polymer obtained by pre-polymerizing with the above monomer and a polyol in the presence of a radical generator An example is a method of graft polymerization.

It is also possible to use a combination system of two or more of these polyols, such as a combination system of a polyether polyol and a polymer polyol (weight ratio, for example, 95:5 to 5:95).

Among these polymeric polyols, preferred are polyether polyols, polymer polyols which are attracted by polyether polyols, and combinations thereof.

Among these, those having primary OH at the terminal are particularly preferred. The terminal primary OH content is usually 10-8
0%, preferably 30-70%. Polyether polyols or polymer polyols with OH terminals include those containing oxyethylene chains at the terminals (chipped type, balanced type), and the content thereof is usually 5 to 30.
% (weight %, the same applies hereinafter) is preferably 10 to 20%. By using a polyol containing a terminal oxyethylene chain in the above range, the moldability of the foam (curing property when depressed, shape due to blistering or shrinkage) ) and the physical properties of the foam are just suitable for this application.

The molecular weight and hydroxyl value of the polyol used are determined by the purpose.

Various changes can be made depending on the required performance.

Two or more polyols having different hydroxyl values may be used in combination. The polyol used for producing HR foam usually has an equivalent weight (molecular weight per hydroxyl group) of 1000 to 2.
500. Preferably 1500-2000. Terminal primary OH
Polyether polyols having a content of usually 10 to 80%, preferably 50 to 70%, and a functional group number of 3 or more, preferably 3 to 6 are suitable.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. For example, aliphatic polyisocyanates (such as hexamethylene diisocyanate lysine diisocyanate)% cycloaliphatic polyisocyanates (1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate).

isophorone diisocyanate, etc.], aromatic polyisocyanates [tolylene diisocyanate (hereinafter abbreviated as TDI), diphenylmethane diisocyanate (hereinafter kfD)
(abbreviated as I)], naphthylene diisocyanate, xylylene diisocyanate, etc.], and mixtures thereof. Among these, aromatic polyisocyanates are preferred, and particularly preferred are TDI, ~fD
I and mixtures thereof. These polyisocyanates are crude polyisocyanates such as crude TDI
, crude MDI L crude diaminodiphenylmethane (a condensation product of formaldehyde and an aromatic amine or a mixture thereof) and a small amount (e.g. 5
Phosgene compound (mixture with ~20i%) of trifunctional polyamine or more: polyallyl polyisocyanate C
PAPI) or modified polyisocyanates such as liquefied MDI (carbodiimide-modified, trihydrocarbylphosphate-modified, etc.) or free isocyanenite-containing powders obtained by reacting excess polyisocyanates (TDI, MDI or modified products thereof, etc.) with polyols. It can be used as a prepolymer, or they can be used in combination (for example, a modified polyisocyanate and a prepolymer are used in combination).The polyol used for producing the above prepolymer usually has an equivalent weight of 30 to 200, such as ethylene glycol. Propylene glycol, diethylene glycol.

Examples include glycols such as dipropylene glycol, triols such as glycerin, high-functional polyols such as pentaerythritol, and sorbitonil; and AO (EO and/or PO) adducts thereof. The free isocyanate group content f of the above-mentioned modified polyisocyanate and prepolymer is usually 15 to 30%.
Preferably it is 20-30%. When it is less than 15%, the viscosity of the isocyanate becomes high. T for HR form
A combination of DI or TDI and AID I is preferred.

In fy: I6, the blowing agent is water and/or a halogen-substituted aliphatic hydrocarbon blowing agent such as trichlorofluoromethane, dichlorodifluoromethane, trichloroethane, trichloroethylene.

Examples include tetrachloroethylene, methylene chloride, trichlorotrifluoroethane, dibromotetrafluoroethane, carbon tetrachloride, and the like. A combination of halogenated hydrocarbons and water is preferred (especially for low density foams).

As other aids! Examples include foaming agents and flame retardants.

Examples of foam stabilizers include silicone surfactants such as siloxane-oxyalkylene block copolymers.

Examples of combustion agents include phosphorus and/or halogen-containing compounds (tris monochloroethyl phosphate, tris dichloropyr phosphate).

Tris dibromopropyl phosphate, tris monobromoethyl phosphite, tris monobromo monochlorophosphite, diammonium rum phosphate, etc.], antimony oxide, etc.

The amount of catalyst used in the present invention is usually 0.05 to 2 parts, preferably 0.1 to 1.5 parts, based on 100 parts of the total of polyol and reticulating agent.

In the present invention, the amount of the reticulating agent used can be varied depending on the molecular weight of the polyol, purpose, required performance, etc. When producing HR foam, the amount of the reticulating agent of the present invention used is usually 0.5 to 10 parts, preferably 1 to 5 parts, per 100 parts (by weight, the same applies hereinafter) of the polyol.
parts, equivalent ratio usually 1:02 to 1:4.2, preferably 1
:04-1 :2.0. If the amount of the reticulating agent is less than the above range, the hardness of the HR foam will not increase,
It becomes impossible to demold the mold in a short time, and if the amount exceeds the above range, the good feel peculiar to HR foam is lost, the foam becomes too hard, and the drop in elongation is large, making it unsuitable as a cushioning material.

In the present invention, when reacting an organic polyisocyanate, a polyol, and a network agent in the presence of a blowing agent, a catalyst, etc., the polyisocyanate and an active hydrogen atom-containing compound (polyol, network agent, etc.) are reacted.

(water) can be varied depending on the required physical properties. Isocyanate index 70-130 [especially 80
A normal 1-1R foam can be manufactured with a diameter of about 120).

The amount of blowing agent can be varied over a wide range depending on the required physical properties and foam density. For low density foams, typically 2.0 parts per 100 parts total of polyol and reticulating agent.
~4.5 parts (preferably 2 to 3.5 parts), polyol,
The amount is 1.2 parts or more (preferably 143 to 3.5 parts) based on 100 parts of the total of the reticulating agent and polyisocyanate. If the amount of water is less than the above, the physical properties of the foam, such as hardness, tensile strength, and tear strength, will deteriorate. For high density foams, usually 0.5 to 2.5 parts (preferably 1 to 2 parts) per 100 parts of polyol and reticulating agent, and 0.3 parts per 100 m of polyol, reticulating agent and polyisocyanate. ~2 parts (preferably 0.7 to 1.5 parts).

The amount of foam stabilizer is usually 02 to 5.0 parts, preferably 0.3 to 3 parts, based on 100 parts of the total of polyol and reticulating agent.

The amount of the combustible agent varies depending on the type thereof and the degree of flame retardation required, physical properties, etc., but it is usually 20% or less, preferably 4 to 15%, of the total amount of the polyol and the reticulating agent. In the case of phosphorus compounds, the phosphorus content in the foam is usually 0.5.
-3%, preferably 1.0-2%.

The method of producing urethane foam in the present invention uses a specific reticulating agent and a specific catalyst;
It may be the same as the conventionally known method, for example, "polyurethane"
(published by Maki Shoten) and "Polyurethanes Chemistry and Technology" (written by Salanders). The foam may be manufactured by a one-shot method or by a prepolymer method (quasi-prepolymer method). In addition, there are various foaming methods such as RIM method (reaction injection mold method), molding other than RIM method (open mold molding, PVC integral molding method, vacuum molding, etc.), slab method, spray method/injection, coating, etc. can be given. The production of HR foam was published in "Journal of Cellular Plastics" July/August (1
974) 171 pages and below, Special Publication No. 53-44192,
JP-A-52-12299, JP-A-51-63896, JP-A-58-J799, JP-A-50-145495
No., Special Publication No. 54-4756, Special Publication No. 54-4'iST
This can be carried out by the method described in the publication.

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The reticulating agent/catalyst, polyol, and polyisocyanate used in the Examples and Comparative Examples are as follows.

Networking agent A: 2-amino-2-ethyl-1,3-propanediol Networking agent B: 2-amino-2-ethyl-1,3-propanediol and oleic acid (molar ratio 110.5) are reacted. The resulting mixture.

Reticulating agent
00 polyether polyol.

Mixed with glycerin. (weight ratio 1/1) Catalyst A: 1,8.5-tris(3-dimethylaminopropyl)hexahydro-5-triazine catalyst X nitriethylenediamine catalyst Y: NIAX, A=1 (manufactured by Union Carbide) )miz: Tetramethylethylenediamine catalyst
U: TOYOCAT-TF (manufactured by Toyo Soda Kogyo Co., Ltd.)
Catalyst V Nitriethylamine catalyst W: N-methylmorpholine polyol I: Polyether polyol obtained by adding 20% EO to glycerin, pentaerythritol and sucrose (OHgfJ=34, EO content 10-13%) polyol ■: Polymer polyol obtained by polymerizing acrylonitrile (202% by weight) in a polyether triol (EO content 13-15%) with a molecular weight of 5000 obtained by adding glycerin PO and then EO (OH value = polyisocyanate I) :80 between TDI and crude MDI
/20 mixture foam stabilizer 1: 5RX-274C()-
(manufactured by Les Silicones) Example 1 and Comparative Example 1.2.8 According to the foaming recipe shown in Table 1, the reticulating agent 1 polyol, catalyst, foam stabilizer and blowing agent were mixed and uniformly dispersed, Next, polyisocyanate was quickly added thereto, stirred for a few seconds, poured into a 30 x 30 x 5 cm aluminum mold, foamed, and cured at 100° C. for 8 minutes.

Table 1 shows the physical properties of the obtained HR foam. The test method for the foam physical properties is as follows.

Total density JIS k-6401 hardness compressive strength) η 1 (-6401 tensile strength N
k-6402 Tear strength JIS k-6402 Elongation #k-6402 Compression water strain '1k-6401 Resilience modulus N k-6401 Moist heat set
"k-6401" It can be seen that the sample obtained according to the present invention is superior in foam hardness and curing property compared to that of the comparative example.

Example 2 and Ratio Example 4.5.6.7.8 A foam was produced in the same manner as in Example 1 using the formulation shown in Table 2, and the effects of catalyst type, foam hardness, and curing properties were determined. We investigated the impact. The results are shown in Table 2.

By using a specific catalyst in combination, the sample obtained according to the present invention can exhibit even more excellent foam hardness and foam curing properties.

Examples 8.4.5 and Comparative Examples 9, 1, and 11 Foams were produced in the same manner as in Example 1 using the formulations shown in Table 3, and the effects on the NCO index and physical properties of the foams were investigated. However, the mold used was an aluminum mold of 30 x 30 x 10 cm.

The results are shown in Table 3.

The samples obtained in the present invention can have a wide range of foam hardness by changing the NGO index compared to that of the comparative example. In particular, it can be seen that when the NGO index is increased, the foam hardness tends to increase.

Example 6 Reticulating agent B was used instead of reticulating agent A in Example 1. The outside was foamed in the same manner as in Example 1. Table 4 shows examples of characteristic values compared with Example 1. Table 4 [Effects of the Invention] The present invention has the following effects.

(1) HR-foam can be obtained that exhibits hardness and can be demolded in a short time.

(2) Even if the NGO index of the organic polyisocyanate and the active hydrogen atom-containing compound (polyol, reticulating agent, water) is high, it is 1. A foam with better curing properties can be obtained compared to the conventional HR foam. Therefore, by simply changing the NGO index, the foam hardness can be varied over a very wide range, and application to foams with different hardness is possible.

(3) The foam has good curing properties. Therefore, there is a big advantage in terms of increasing productivity.

(4) In the case of conventional (IR) foam, a major drawback is that when it is made into a low density foam, it becomes insufficient in hardness. However, since the present invention can provide sufficient foam hardness, it has become possible to apply it to low-density foams.

(5) The problem is that 2-amino-2-ethyl-1,3-propanediol represented by general formula (2) in the present invention causes crystallization as in the case of using trimethylolaminomethane, making it difficult to use. There are no points.

Claims (1)

[Claims] 1. A method for producing urethane foam by reacting an organic polyisocyanate, a polyol, and a reticulating agent in the presence of a blowing agent, a catalyst, and, if necessary, other auxiliary agents, in which one of the catalysts is As a part, there are general formulas, numerical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R_1 and R_2 represent an alkyl group). A method for producing highly elastic urethane foam characterized by using a primary amine and/or its derivative represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (2) (In the formula, R represents an alkyl group.) . 2. The manufacturing method according to claim 1, wherein R_1 in general formula (1) is an alkyl group having 2 or more carbon atoms. 3. The method according to claim 1 or 2, wherein the amine catalyst is 1,3,5-tris(3-dimethylamino-propyl)-hexahydro-s-triazine. 4. The production method according to any one of claims 1 to 3, wherein the primary amine derivative in general formula (2) is a salt or an amide. 5. The production method according to any one of claims 1 to 4, in which the primary amine and/or its derivative is used in an amount of 0.4 to 2.0 equivalents based on the hydroxyl group equivalent of the polyol. . 6. The primary amine is 2-amino-2-ethyl-1,3-
The manufacturing method according to any one of claims 1 to 5, which is propanediol. 7. Claims 1 to 7, wherein the polyol is a polyether polyol and/or a polymer polyol.
The manufacturing method according to any one of paragraph 6. 8. The production method according to any one of claims 1 to 7, wherein the polyol has 10 to 80% of terminal primary hydroxyl groups.