JP2000248033A - Production of polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing even at relatively low temperatures a polyurethane foam excellent in mechanical properties with addition- polymerized segment and polyurethane segment crosslinked with each other. SOLUTION: This method for producing a polyurethane foam comprises polymerization between an addition-polymerizable active hydrogen component consisting of A1 or A2 described below and an organic polyisocyanate in the presence of a polymerization initiator consisting of a peroxide, transition metal- contg. compound, chelating agent and/or reducing agent, in the presence or absence of an auxiliary to carry out polymerization of addition-polymerizable functional groups along with polyurethane formation reaction; A1: a compound (a) having active hydrogen-contg. group and addition-polymerizable functional group; A2: two or more kinds of compounds selected from the compound (a), a compound b having addition-polymerizable functional group but no active hydrogen-contg. group, and compound c having active hydrogen-contg. group but no addition-polymerizable functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyurethane foam having excellent mechanical properties and a method for producing the same.
More specifically, it is a foam structure in which a polymer chain portion (abbreviated as an addition polymerization portion) formed by an addition polymerization reaction and a polyurethane portion are cross-linked to each other. The present invention relates to a polyurethane foam having characteristics excellent in mechanical properties and having characteristics of mechanical properties such as small compression set when a flexible foam is formed.

[0002]

2. Description of the Related Art Conventionally, a polyurethane foam having an addition-polymerized portion and a polyurethane portion has been disclosed in Japanese Unexamined Patent Publication No. Hei.
No. 244620 and JP-A-63-23956. In these documents, a polymerization initiator, specifically, a radical free radical generator such as a peroxide or an azo compound is used to carry out addition polymerization of an addition-polymerizable functional group. However, in these methods, when the addition polymerization reaction is carried out at a low temperature, specifically at room temperature to 80 ° C., it is necessary to use a radical free radical generator having a low half-life temperature. There were problems such as the need to store the free radical generator at a low temperature. In order to solve this problem, when a so-called redox polymerization initiator comprising a combination of a peroxide and an inorganic metal salt described in JP-A-49-109496 is used as a radical free radical generator, Although the problem of storage stability of is solved, the inorganic metal salt does not dissolve in the polyurethane foam raw material system at the time of polyurethane foam production, so radical free radicals are not effectively generated, the reaction rate of the addition polymerization reaction decreases, There was a problem that mechanical properties such as foam hardness and dimensional stability of the obtained polyurethane foam deteriorated.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyurethane foam having excellent storage stability of raw materials and a polyurethane foam having excellent mechanical properties even when produced at a low temperature. Is to provide a method for producing a mutually crosslinked polyurethane foam.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the problems can be solved by using a polymerization initiator in which specific components are combined, and have reached the present invention.

That is, the present invention provides an addition-polymerizable active hydrogen component (A) comprising the following (A1) or (A2), an organic polyisocyanate (B), a peroxide (d) and a transition metal-containing compound (A). e) in the presence of a polymerization initiator (C1) comprising a chelating agent (f) and / or a reducing agent (g), in the presence or absence of an auxiliary agent (D), to form an addition-polymerizable functional group. (A1): a compound having an active hydrogen-containing group and an addition-polymerizable functional group (a) (A2): an active hydrogen-containing group and an addition polymerizable It comprises a compound (a) having a functional group, a compound (b) having an addition-polymerizable functional group and having no active hydrogen-containing group, and a compound (c) having an active hydrogen-containing group and having no addition-polymerizable functional group. Selected from the group Polymerization of two or more compounds, an addition-polymerizable active hydrogen component (A) composed of the above (A1) or (A2), and an organic polyisocyanate (B) with a water-soluble hydroperoxide (d1) A method for producing a polyurethane foam, comprising conducting a polyurethane-forming reaction together with the polymerization of an addition-polymerizable functional group in the presence of an agent (C2), in the presence or absence of an auxiliary agent (D); A polyurethane foam obtained by the method; and an automobile shock absorbing material, an automobile handle material, an automobile seat cushion material, an automobile seat back material, or an automobile headrest material comprising the polyurethane foam.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerization initiator (C) used in the present invention
A polymerization initiator (C1) comprising a peroxide (d) and a transition metal-containing compound (e) as essential components, and a chelating agent (f) and / or a reducing agent (g) in addition thereto. , Water-soluble hydroperoxides (d
The polymerization initiator (C2) comprising 1) is used. In the present invention, the peroxides (d) used as an essential component in (C1) include the following (d1) to (d7), and two or more thereof may be used in combination. (D1) Water-soluble hydroperoxides: for example, methyl hydroperoxide, ethyl hydroperoxide, n-propyl peroxide, t-butyl hydroperoxide, etc. (d2) Water-insoluble hydroperoxides: for example, hydroxyheptyl Peroxide, cumene hydroperoxide, p-menthane hydroperoxide, 2,5
-Dimethyl-2,5-dihydroperoxyhexane,
(D3) Ketone peroxides: for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, etc. (d4) Diacyl peroxides: For example, acetyl peroxide, propionyl peroxide, lauroyl peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, etc.

(D5) Dialkyl peroxides: For example, di-t-butyl peroxide, di-t-amyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, etc. (d6) alkyl peresters: for example, t-butyl peracetate, t -Butyl peroctoate, t-butyl perpivalate, di-t-butyl-diperphthalate, t-butyl perbenzoate, 2,5-dimethyl (2,5-dibenzoylperoxy) hexane, 2,5
-Dimethyl (2,5-dibenzoylperoxy) hexine-3, t-butyl permaleate, di-t-butyl peroxyoxalate, acetylcyclohexylsulfonyl peroxide, etc. (d7) Other peroxides: for example, isopropyl Percarbonate, t-butyl peroxyisopropyl carbonate, succinic peroxide, 2,5-dimethyl-3-hexyne-2,5-diperoxyisopropyl carbonate, etc. Among these, from the viewpoint of the reaction rate of the addition polymerization reaction And hydroperoxides [(d1) and (d2)] are preferred. As the polymerization initiator (C2), the above (d)
1) is used alone.

In the present invention, the transition metal-containing compound (e) used as an essential component in (C1) is preferably a compound that does not promote the urethanization reaction.
An inorganic acid salt, an organic acid salt, a hydroxide or an organic complex (such as a cyclopentadienyl compound) of at least one metal selected from the group consisting of iron, cobalt, manganese, vanadium, and cerium. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, and examples of the organic acid include acetic acid, naphthenic acid, octenoic acid, and acrylic acid. Specific examples of the transition metal-containing compound (e) include inorganic acid salts such as ferrous sulfate and ferric sulfate, cobalt nitrate, and iron chloride; cobalt naphthenate, iron naphthenate, iron octenoate, and manganese naphthenate. And organic complexes such as ferrocene. From the viewpoint of economy, ferrous sulfate is preferred.

The chelating agent (f) in the present invention is not particularly restricted but includes nitrogen-containing chelating agents such as ethylenediaminetetraacetic acid, ethylenediamine, nitrilotriacetic acid and 1,10-phenanthroline.
Ethylenediaminetetraacetic acid is particularly preferred from the viewpoint of the rate of the addition polymerization reaction.

The reducing agent (g) in the present invention includes, for example, sulfites, thiosulfates and sulfonates, and includes SO ₂ , NaSO ₃ , NaHSO ₃ and NH ₄ HS.
O ₃ , Na ₂ S ₂ O ₃ , Na ₂ S ₂ O ₄ , Na ₂ S ₂ O ₇ , dithionite, Et ₂ SO ₃ , diethyl sulfoxide, p-toluenesulfonic acid, formaldehyde sodium sulfoxylate (Rongalit) and the like No. From the viewpoint of the rate of the addition polymerization reaction, sulfites are preferred, and Rongalite is particularly preferred.

The combination of the polymerization initiator (C) used in the present invention includes the following four combinations. Water-soluble hydroperoxide (d1) alone Peroxides (d) and transition metal-containing compound (e)
And chelating agent (f) peroxides (d) and transition metal-containing compound (e)
And reducing agent (g) peroxides (d) and transition metal-containing compound (e)
And a chelating agent (f) and a reducing agent (g). Of the above combinations, (f) is added for the purpose of improving the solubility and storage stability of (e) in the polyurethane foam raw material system during production, g) serves to reduce the oxidized (e). When (f) and / or (g) is absent in the combination of (i.e., polymerization initiator (C1)) [except when (d) is (d1)], radical release in the foam is There is a problem that the concentration of the group is reduced and the mechanical strength of the foam is reduced. Among these combinations, it is preferable from the viewpoint of the effect of polymerization initiation. In addition, [the polymerization initiator (C2)] is preferable in that the amount of the components is reduced and the production becomes easier.

In the above case, among the peroxides (d), the water-soluble hydroperoxides (d1) are a transition metal-containing compound (e) and a chelating agent (f) and / or a reducing agent (g). Promotes the polymerization reaction in urethane foam even in the absence. From the viewpoint of the conversion of the addition polymerization reaction, t-butyl hydroperoxide is particularly preferred. The amount of (d1) used is preferably (d1): the number of moles of the addition-polymerizable functional group in the addition-polymerizable active hydrogen component (A) = 1: 0.001 to 100.

In the above combination, the peroxides (d) and the transition metal-containing compound (e) when used are used.
The molar ratio of the chelating agent (f) to the chelating agent (f) is usually (d) :( e) :( f) = 1: 0.001 to 3: 0.0
01-3. (D): (e): (f) = 1: 0.0
05-1: 0.005-1 is preferred. When the molar ratio of each component is less than or equal to the upper limit of the above range, the solubility in the reaction system is good, and there is no adverse effect on the urethanization reaction. In the case of d), the effect as a polymerization initiator is large.

In the case of any of the above combinations, the peroxides (d) and the transition metal-containing compound (e) when used are used.
The molar ratio of the reducing agent (g) to the amount of the reducing agent (g) is usually (d):
(E): (g) = 1: 0.001-3: 0.001-3
It is. (D): (e): (g) = 1: 0.005-
1: 0.005 to 1 is preferred. When the molar ratio of each component is not more than the upper limit of the above range, the solubility in the reaction system is good, without adversely affecting the urethanization reaction,
If it is not less than the lower limit of the above range, in the case of (d) other than (d1), the effect as a polymerization initiator is large.

In the case of any of the above combinations, the peroxides (d) and the transition metal-containing compound (e) when used are used.
The molar ratio of the chelating agent (f) to the reducing agent (g) is usually (d) :( e) :( f) :( g) = 1: 0.
001-3: 0.001-3: 0.001-3.
(D): (e): (f): (g) = 1: 0.005-
1: 0.005 to 1: 0.005 to 1 are preferred. When the molar ratio of each component is equal to or less than the upper limit of the above range, the solubility in the reaction system is good, and there is no adverse effect on the urethanization reaction.
In the case of (d) other than 1), the effect as a polymerization initiator is large.

In the above cases (1) to (4), the amount used in the raw material of the polyurethane foam is a mole of the peroxide (d) and the number of moles of the addition-polymerizable functional group in the addition-polymerizable active hydrogen component (A) described later. In a ratio, the molar number of the addition-polymerizable functional group in (d) :( A) is usually 1:10 to 2000.
(D): mole number of addition polymerizable functional group in (A) = 1: 1
0 to 1000 is preferred. When the molar ratio of (A) to (d) is within the above range, the solubility of (d) in the reaction system is good, the urethanization reaction is not adversely affected, and the effect as a polymerization initiator is large. .

The addition-polymerizable active hydrogen component (A) in the present invention comprises the following (A1) or (A2). (A1): Compound (a) having an active hydrogen-containing group and an addition polymerizable functional group (A) (A2): Compound (a) having an active hydrogen-containing group and an addition polymerizable functional group Two or more compounds selected from the group consisting of a compound (b) having no hydrogen-containing group and a compound (c) having an active hydrogen-containing group and having no addition-polymerizable functional group

In the production method of the present invention, the addition polymerizable functional group (x) of (a) includes a radical polymerizable functional group of terminal olefin type or internal olefin type, a cationic polymerizable functional group (vinyl ether group, propenyl ether group). And the like, and one or more groups selected from anionic polymerizable functional groups (such as a vinyl carboxyl group and a cyanoacryloyl group). Among these, a radical polymerizable functional group is preferable, and a terminal olefin type radical polymerizable functional group represented by the following general formula [1] is more preferable. (Wherein, R represents hydrogen, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 21 carbon atoms.) Specific examples of the group having the group represented by the general formula [1] include And an acryloyl group, a methacryloyl group, a vinyl group, a vinylbenzyl group, a vinylphenyl group and an allyl ether group. Among these groups, an acryloyl group, a methacryloyl group and an allyl ether group are particularly preferred. The number of addition-polymerizable functional groups in (a) is usually 1 to 10, preferably 1 to 5. The active hydrogen-containing group (w) contained in (a) is not particularly limited, and is, for example, at least one active hydrogen selected from a hydroxyl group, a mercapto group, a carboxyl group, a primary amino group, a secondary amino group, and the like. Included groups. Preferred active hydrogen containing groups are hydroxyl groups and mercapto groups. The number of active hydrogen-containing groups in (a) is usually 1 to 8, preferably 1 to 5.

As (a), those represented by the following formula [2] are more preferable. (Where R represents hydrogen, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 21 carbon atoms, X is O, S or NH, p and q are positive integers, and Q is active As the hydrogen-containing group, Z represents a residue obtained by removing p + q active hydrogen-containing groups from the active hydrogen compound.) R is preferably a hydrogen or alkyl group, particularly preferably a hydrogen or methyl group, and X is preferably O. . The value of p is preferably 1 to 7, more preferably 1 to 5, and the value of q is preferably 1 to 7, more preferably 1 to 4. In the case of a flexible foam to be described later, since the concentration of the addition-polymerizable functional group and the active hydrogen-containing group is low, if q is less than 2, the resulting foam may have low elongation and tear strength. Is particularly preferably 2 to 4. Also p
The value of + q is preferably 2 to 8, and more preferably 3 to 8 for flexible foams. Further, Q is preferably a hydroxyl group.

As a specific example of the above (a), the following (a)
1) to (a4), and two or more kinds may be used in combination. (A1) Polyols [Polyhydric alcohols; Polyhydric phenols; Polyols obtained by adding alkylene oxide (AO) thereto; Polyols obtained by adding (AO) to amines; Derived from polyhydric alcohols and polycarboxylic acids (A2) Unsaturated carboxylic acid partial amidates of amines (a3) Unsaturated carboxylic acid partial thioesters of polythiols (a4) Vinyl monomers having a hydroxyl group

Among the polyols used in the production of (a1), polyhydric alcohols include, for example, those having 2 to 18 carbon atoms.
(Preferably 2 to 12) dihydric alcohols [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4- and 1,3
-Butanediol, 1,6-hexanediol, neopentyl glycol, etc.], having 3 to 18 carbon atoms (preferably 3
To 12) trihydric or higher hydric alcohols [glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannyl, glucose, fructose, sucrose, etc.] Combinations of more than one species may be mentioned.

Among the polyols used in the production of (a1), polyhydric phenols include, for example, hydroquinone, bisphenols (bisphenol A, bisphenol F, etc.), formalin low-condensates of phenol compounds (intermediates of novolak resins and resols). Body) and combinations of two or more of these.

Among the polyols used in the production of (a1), the amines in the polyether polyol obtained by adding AO to the amines include, for example, ammonia; alkanolamines [mono-, di- or triethanolamine, isopropanol; Amines, aminoethylethanolamine, etc.]; alkylamines having 1 to 20 carbon atoms [methylamine, ethylamine, n-butylamine, octylamine, etc.]; alkylenediamines having 2 to 6 carbon atoms [ethylenediamine, hexamethylenediamine, etc.] ;
Polyalkylene (C2-6) polyamines [diethylenetriamine, triethylenetetramine, etc.]; C6-20 aromatic amines [aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine, etc. Alicyclic amines having 4 to 15 carbon atoms [isophoronediamine, cyclohexylenediamine, etc.]; heterocyclic amines having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine] Etc.] and a combination of two or more of these.

Alkylene oxide (AO) added to polyhydric alcohols, polyphenols or amines
As ethylene oxide (hereinafter abbreviated as EO),
Propylene oxide (hereinafter abbreviated as PO), 1,2
-, 1,4- or 2,3-butylene oxide, styrene oxide and the like and a combination of two or more of these (when used in combination, random addition or block addition may be used), but only these are included. However, the present invention is not limited to this. Preferred of these are PO
And / or EO as a main component and 20% by mass or less of another alkylene oxide. The addition reaction can be performed by a conventionally known ordinary method.
The number of moles of AO added is preferably from 1 to 70, and more preferably from 2 to 50.

Among the polyols used in the production of (a1), the polyhydric alcohols used for the polyester polyol include the same ones as described above. Examples of the polycarboxylic acids include aliphatic polycarboxylic acids having 4 to 18 carbon atoms. Acids [succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, etc.], aromatic polycarboxylic acids having 8 to 18 carbon atoms [phthalic acid or its isomers, trimellitic acid, etc.],
Ester-forming derivatives of these polycarboxylic acids [acid anhydrides, lower alkyl esters having 1 to 4 carbon atoms in the alkyl group, etc.] and combinations of two or more of these.

As the polyols used in the production of (a1), those having 2 to 8 (particularly 2 to 6) hydroxyl groups and an OH equivalent of 30 to 1200 (particularly 31 to 250) are preferable. (A1) is obtained by partially esterifying the polyols exemplified above with an unsaturated carboxylic acid in an equivalent ratio such that at least one hydroxyl group remains in one molecule without being reacted. Unsaturated carboxylic acids include (meth) acrylic acid, crotonic acid,
Maleic acid, fumaric acid, itaconic acid, citraconic acid,
Mesaconic acid, anionic acid, cinnamic acid, vinylbenzoic acid, etc., and a combination of two or more of these [where (meth)
Acrylic acid means acrylic acid and / or methacrylic acid, and the same description method will be used hereinafter. Ester-forming derivatives of these unsaturated carboxylic acids, such as halides (such as (meth) acrylic acid chloride), acid anhydrides [such as maleic anhydride, itaconic anhydride, citraconic anhydride]; In combination of two or more.

Specific examples of the compound (a1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 3-phenoxy-2-hydroxypropyl (meth) ) Acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol mono (meth) acrylate,
Pentaerythritol triacrylate and the like, and a combination of two or more of these.

In (a2), among the above amines, a polyamine or an alkanolamine and the above unsaturated carboxylic acid are obtained by reacting at least one amino group or hydroxyl group (in the case of alkanolamine) in one molecule. By reacting in an equivalent ratio such that Specific compounds include (meth) acrylamidoethylamine, (meth) acrylamidohexylamine, and the like, and combinations of two or more of these.

The polythiols used for the production of (a3) are preferably those having 2 to 4 thiol groups and having 2 to 18 carbon atoms, for example, ethanedithiol, 1,2-propanedithiol, 1,3- Propanedithiol, 1,
4-propanedithiol, 1,4-benzenedithiol, 1,2-benzenedithiol, bis (4-mercaptophenyl) sulfide, 4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate, trimethylolpropane Tris (thioglycolate) thiocyanuric acid, di (2-mercaptoethyl) sulfide, di (2-mercaptoethyl) ether, and a combination of two or more of these.

(A3) is obtained by reacting these polythiols with the above-mentioned unsaturated carboxylic acids in an equivalent ratio such that at least one thiol group remains unreacted in one molecule. Specific compounds include acryloylthioethylmercaptan, acryloylthiobutylmercaptan, and the like, and combinations of two or more of these.

Examples of (a4) include p-hydroxylstyrene, (meth) allyl alcohol, cinnamyl alcohol, crotonyl alcohol, partially allyl etherified products of the above-mentioned polyhydric alcohols (pentaerythritol triallyl ether, etc., in one molecule). Those having at least one hydroxyl group), the above-mentioned alkylene oxide (AO) adducts of these compounds (preferably 2 to 20 mol adducts), and combinations of two or more of these. The number of addition-polymerizable functional groups (a4) is preferably 1 to 5, the number of active hydrogen-containing groups is preferably 1 to 5, and the molecular weight is preferably 1,000 or less.

Preferred among these are unsaturated carboxylic acid partial esters (a1) of polyols and vinyl monomers having a hydroxyl group, since the viscosity is low when the composition for forming a polyurethane is low. (A4) (especially allyl etherified products of polyhydric alcohols), particularly preferably an unsaturated carboxylic acid partial ester of a polyhydric alcohol or an alkylene oxide adduct thereof, and most preferably diethylene glycol mono (meth) acrylate. It is.

The molecular weight per active hydrogen-containing group (a) is preferably from 40 to 2500, more preferably from 40 to 500 in consideration of the viscosity of the composition for forming a polyurethane. Preferably 45 to 40
0.

(B) in the present invention is a compound having an addition-polymerizable functional group (x) and having no active hydrogen-containing group (w). As the addition-polymerizable functional group of (b), the same as the addition-polymerizable functional group in the compound (a) can be mentioned, and a radical-polymerizable functional group is preferable. Specific examples of the radical polymerizable functional group include an acryloyl group, a methacryloyl group, a vinyl group, a vinylbenzyl group, a vinylphenyl group, an allyl ether group, and the like. Preferred radically polymerizable functional groups are represented by the following general formula (1) as in (a):
And particularly preferred are an acryloyl group, a methacryloyl group and an allyl ether group.

The number of addition-polymerizable functional groups in (b) is usually 1
10 to 10, preferably 1 to 8, and when importance is attached to improvement of mechanical strength, the number of addition-polymerizable functional groups in (b) is
It is preferably 2 to 8, particularly 4 to 8. Considering the reduction in the viscosity of the composition for forming a polyurethane, the viscosity of (b) is preferably 1,000 mPa · s (25 ° C.) or less, particularly 500 mPa · s (25 ° C.) or less. Further, (b) may be used in the component (A2) together with (a) as a by-product produced simultaneously with the production of (a).

As a preferred specific example of (b), the following (b)
1) to (b6), and combinations of two or more of these. (B1) polyols [polyhydric alcohols; polyhydric phenols; polyether polyols obtained by adding alkylene oxide (AO) thereto; polyether polyols obtained by adding (AO) to amines; polyhydric alcohols and polycarboxylic acids (B2) Unsaturated carboxylic acid amidates of amines (b3) Unsaturated carboxylic acid thioesters of polythiols (b4) Aromatic hydrocarbon monomers (B5) Unsaturated nitriles (b6) (Meth) acrylates

(B1) can be obtained by reacting a monool or a polyol with the unsaturated carboxylic acid used in the production of (a1) described above, while changing the molar ratio in the case of obtaining (a1). Examples of usable monools include monohydric alcohols having 1 to 8 carbon atoms [methanol, ethanol, propanol, butanol, hexanol, etc.]; monohydric phenols having 6 to 12 carbon atoms [phenol, 4-methylphenol] Etc.]; and their alkylene oxide adducts. As the polyols that can be used, those similar to the polyols that can be used when producing the above (a1) can be used.

(B2) is used for the production of (a2).
It can be obtained by reacting a polyamine or alkanolamine with an unsaturated carboxylic acid with (a2) in a different molar ratio. (B3) can be obtained by reacting a polythiol and an unsaturated carboxylic acid used in the production of the above (a3) with (a3) in a different molar ratio. Examples of (b4) include aromatic hydrocarbon monomers having 8 to 20 carbon atoms, such as styrene, α-methylstyrene, and chlorostyrene. (B5) includes (meth) acrylonitrile and the like. As (b6), alkyl (meth) acrylates (where the alkyl group has 1 to 3 carbon atoms)
0) [Specifically, methyl (meth) acrylate, butyl (meth) acrylate, decyl (meth) acrylate,
Hexadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.].

(C) has an active hydrogen-containing group (w),
At least one compound having no addition-polymerizable functional group (x). (C) is usually (average) 2 or more, more preferably (average) 2.5 or more, and particularly preferably 3 to 3.
It has eight active hydrogen-containing groups. When the (average) number of active hydrogen-containing groups is 2 or more, the mechanical properties such as hardness and dimensional stability are good when a semi-rigid foam is formed, and the compression set is small when a flexible foam is formed. Become.

The active hydrogen-containing group (w) in (c) includes at least one active hydrogen-containing group selected from a hydroxyl group, a mercapto group and an amino group.
As a preferred example of (c), a compound having an active hydrogen-containing group selected from a hydroxyl group, a mercapto group and an amino group, more preferably a compound having 2 to 8 (particularly 3 to 8) hydroxyl groups and / or mercapto groups And
Particularly preferred are at least one polyol selected from the group consisting of polyether polyols and polyester polyols.

As the polyether polyol, a known polyether polyol usually used for polyurethane foam, for example,
Examples of the polyether polyol include the above-mentioned polyhydric alcohols, polyhydric phenols, polycarboxylic acids, amines, and the like, to which the above-mentioned alkylene oxide (AO) is added. Preferred as AO are PO and / or E
O as a main component and 20% by mass or less of another alkylene oxide, particularly preferably PO and / or
Or EO. As polyester polyol,
Known ones usually used for polyurethane foams, for example, polyester polyols derived from the above-mentioned polyhydric alcohols or polyhydric phenols and the above-mentioned polycarboxylic acids are mentioned. Particularly preferred as (c) are polyether polyols obtained by adding AO to polyhydric alcohols. Further, the number average molecular weight of (c) is preferably from 50 to 10000, particularly preferably from 60 to 8000. The OH equivalent of (b) is preferably 30
5,000, more preferably 75-3000.

In the present invention, if necessary, the vinyl polymer (H) can be further dispersed in (c) before use. (H) may be dispersed in (c) after polymerization, but preferably the vinyl monomer (h) is used in (c).
Are polymerized and stably dispersed for use. (H)
For example, acrylonitrile, styrene, vinylidene chloride,
Alkyl (meth) acrylate and the like can be mentioned. Preferably, they are acrylonitrile and styrene. The amount of (H) is usually 5 to 50 parts by mass per 100 parts by mass of (c),
Preferably it is 15 to 45 parts by mass.

(A) and (c) each of the active hydrogen-containing group (w) and the isocyanate group (z) of (B) at a temperature of 1
The reaction rate constant K1 at 20 ° C. is 1 (liter / mol / mol).
(Seconds) or less; (a) and (b) the polymerization reaction rate constant K2 of each addition-polymerizable functional group (x) is 10 (liter / mol / second) or more; and K2 / K1 is 100 or more. It is preferable that

The component (A) is the same as the component (A1) or (A
2), the combination in the case of (A2) is specifically a compound (a) having an active hydrogen-containing group and an addition polymerizable functional group and an active hydrogen-containing group having an addition polymerizable functional group. Compounds (b) and (a) having no active hydrogen-containing group and compounds (c) having no addition-polymerizable functional group (c), (b) and (c), (a) and (b) and (c) There are the following ~
Is preferred. The compound (a) having one active hydrogen-containing group (w) (a11) and the compound (c) having an equivalent weight per active hydrogen-containing group (molecular weight per active hydrogen-containing group) of 40 or more Stuff. And those further containing (b). Compound (a) having two or more active hydrogen-containing groups (w) (a12) and compound (c). And those further containing (b). Compound (a11), compound (a12), and compound (c). And those further containing (b). That is, when the compound (c) used in combination has an equivalent weight per active hydrogen-containing group of 40 or more, the compound (a) has one active hydrogen-containing group (w), but has two or more active hydrogen-containing groups (w) ( a
12) may be used, but when the compound (c) used in combination has an equivalent weight per active hydrogen-containing group of less than 40, the compound (a) has at least two active hydrogen-containing groups (w) (a12). Partial use is preferred. The reason for this is that when a long-chain compound having a low equivalent weight of less than 40 per active hydrogen-containing group is used as the compound (c), crosslinking of the addition-polymerized portion per polyurethane chain length formed does not decrease. In order to achieve this, one active hydrogen-containing group (w) of the compound (a) is insufficient, while the equivalent chain length per active hydrogen-containing group of (c) is 40 or more and the relative chain length is relatively large. In the case of a shorter length, crosslinking of the addition-polymerized portion per polyurethane chain length in which even one active hydrogen-containing group (w) of the compound (a) is formed is ensured. By ensuring cross-linking, when a semi-rigid foam is formed, it has excellent properties such as hardness and dimensional stability, and when a flexible foam is formed, compression set is small. A polyurethane foam having the characteristics of the following mechanical properties is obtained. For the same reason, when only (a11) is used in combination of (a) and (c), the compound (c) having an equivalent weight per active hydrogen-containing group of 60 or more, particularly 100 or more, is used. Is preferred.

The content ratio of the addition polymerizable functional group-containing compound (total of (a) and (b)) in the component (A2) is usually 1 to 100% by mass, more preferably 2 to 100% by mass. For a rigid foam described later, the content is more preferably 5 to 100% by mass, and particularly preferably 10 to 95% by mass.

(B) is usually at most 80% by mass, preferably at most 60% by mass, particularly at most 40% by mass, based on the total mass of (a) and (b).

The ratio of (a) to the total mass of (a) and (c) in each of the above cases is usually 1 to 100% by mass, preferably 2 to 100% by mass, and more preferably 2% by mass.
(A11) and (a1)
The amount of (a12) based on the total mass of 2) is preferably 5% by mass or more, more preferably 20% by mass or more.

As the organic polyisocyanate (B) in the present invention, those conventionally used in polyurethane foams can be used. Such isocyanates include aromatic polyisocyanate (B1), aliphatic polyisocyanate (B2), alicyclic polyisocyanate (B3), and araliphatic polyisocyanate (B
4), modified polyisocyanate (B5) and a mixture of two or more thereof.

Examples of the aromatic polyisocyanate (B1) include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same applies to the following isocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, And isocyanate crude products. (B1)
Examples of 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and 4,4'-diphenylmethane diisocyanate (M
DI), polymethylene polyphenyl isocyanate (crude MDI), naphthylene-1,5-diisocyanate,
Triphenylmethane-4,4 ', 4''-triisocyanate and the like.

Examples of the aliphatic polyisocyanate (B2) include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples of (B2) include 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

Examples of the alicyclic polyisocyanate (B3) include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples of (B3) include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.

Examples of the araliphatic polyisocyanate (B4) include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples of (B4) include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate.

Examples of the modified polyisocyanate (B5) include modified products of (B1) to (B4) (such as carbodiimide-modified, allophanate-modified, urea-modified, buret-modified, isocyanurate-modified, oxazolidone-modified).
Is mentioned. Specific examples of (B5) include urethane-modified MDI, carbodiimide-modified MDI, and urethane-modified TDI.
DI, burette-modified HDI, isocyanurate-modified IPDI, and the like.

Of those exemplified as (B), preferred are TDI, MDI, crude TDI and crude MDI.
One or more organic polyisocyanates selected from DI, urethane-modified TDI, urethane-modified MDI, and carbodiimide-modified MDI.

In the present invention, the addition-polymerizable active hydrogen component (A) and the organic polyisocyanate (B) are converted from the blowing agent (D1) and the additive (D2) in the presence of a polymerization initiator (C). In the presence or absence of at least one auxiliary agent (D) selected from the group consisting of, a polyurethane-forming reaction is carried out together with the polymerization of the addition-polymerizable functional group to obtain a polyurethane foam. In the present invention, performing the polyurethane-forming reaction together with the polymerization of the addition-polymerizable functional group means that the polymerization of the addition-polymerizable functional group and the polyurethane-forming reaction are performed at least partially in parallel. . In order to increase the crosslink density and improve the mechanical properties, it is necessary to start the other reaction before curing and forming the resin in one reaction, and to carry out the two reactions in parallel. Although preferred, the polymerization of the addition-polymerizable functional groups or the polyurethane-forming reaction can be caused sequentially and sequentially.

As the optional foaming agent (D1),
For example, at least one or more selected from hydrogen atom-containing halogenated hydrocarbons, water, low-boiling hydrocarbons, and liquefied carbon dioxide can be used.

Specific examples of the hydrogen atom-containing halogenated hydrocarbon include those of the HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123, HCF
C-141b, HCFC-22 and HCFC-142
b), HFC (hydrofluorocarbon) type (for example, HFC-134a, HFC-152a,
FC-356mff, HFC-236ea, HFC-2
45ca, HFC-245fa and HFC-365m
cf) and the like. Among these, preferred are HCFC-141b, HFC-134a, and HFC-141b.
356mff, HFC-236ea, HFC-245c
a, HFC-245fa, HFC-365mcf and a combination of two or more of these. The low boiling point hydrocarbon is a hydrocarbon having a boiling point of usually -5 to 70 ° C, and specific examples thereof include butane, pentane and a mixture thereof. When a normal rigid urethane foam is formed by foaming agent foaming, (c) is used as a polyol component. However, since low-boiling hydrocarbons have low solubility in (c), low-boiling hydrocarbons are used as blowing agents. In such a case, there are problems that the foaming ratio of the foam is small and the cells tend to be uneven. On the other hand, in the present invention, a polyurethane foam is formed using the component (A). However, when (a) is used as (A), when a low-boiling hydrocarbon is used as the blowing agent (D1), (A) The solubility of the low-boiling hydrocarbon of (a) is high, so that it can be used in large amounts, and the premix of (A) and the blowing agent has good stability.
For this reason, there is an advantage that there is no problem that the expansion ratio of the foam is small or the cells tend to be non-uniform.

When the halogenated hydrocarbon compound containing a hydrogen atom is used, the amount is usually not more than 50 parts by mass, preferably 5 to 45 parts per 100 parts by mass of the component (A).
Parts by weight. When the low-boiling hydrocarbon is used, the amount is usually not more than 45 parts by mass, preferably 5 to 40 parts by mass, per 100 parts by mass of the component (A). When liquefied carbon dioxide is used, the amount used is usually not more than 45 parts by mass, preferably 5 parts by mass, per 100 parts by mass of component (A).
２５25 parts by mass. When the hydrogen atom-containing halogenated hydrocarbon compound and water are used in combination, the amount of the hydrogen atom-containing halogenated hydrocarbon compound is usually not more than 45 parts by mass per 100 parts by mass of the component (A), preferably 5-
40 parts by mass, and the amount of water is usually not more than 10 parts by mass, preferably 0.5 to 100 parts by mass per 100 parts by mass of the component (A).
8 parts by mass. When the low boiling point hydrocarbon and water are used in combination, the amount of the low boiling point hydrocarbon is usually not more than 40 parts by mass, preferably 2 parts by mass, per 100 parts by mass of the component (A).
To 35 parts by mass, and water is usually used in an amount not exceeding 10 parts by mass, preferably 0.5 part by mass, per 100 parts by mass of the component (A).
８8 parts by mass. When liquefied carbon dioxide gas and water are used in combination, the amount of liquefied carbon dioxide gas is usually not more than 25 parts by mass, preferably 0.1 mass part per 100 parts by mass of component (A).
The amount of water is usually not more than 10 parts by mass, preferably 0.1 part by mass, per 100 parts by mass of component (A).
5 to 8 parts by mass. When only water is used alone as the foaming agent, the amount of water to be used is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of component (A).

As the optional additive (D2),
Foam stabilizer (D21), urethanization catalyst (D22), inorganic powder (D23), hollow microspheres (D24), dehydrating agent (D2)
5), short fiber (D26), chain transfer agent (D27), dust scattering reducing agent (D28), and the like. These are, as described below, various embodiments of a foaming agent foamed foam, a mechanical froth foam, and a syntactic foam. At least a part of what is added differs depending on the amount of the compound. Other optional additives (D2) include polymerization inhibitors, organic lubricants (calcium stearate, ethylenediamine stearylamide, oleic acid monoethanolamide, etc.), plasticizers (dioctyl phthalate, dioctyl adipate, etc.), thixotropy Examples include an imparting agent (such as particulate silica), an ultraviolet absorber, an antioxidant, an antioxidant, a coloring agent (dye or pigment), a flame retardant, a fungicide, and an antibacterial agent.

Examples of the foam stabilizer (D21) include all those used in the production of ordinary polyurethane foams, such as a dimethylsiloxane-based foam stabilizer, a polyether-modified dimethylsiloxane-based foam stabilizer, and a phenylmethylsiloxane-based foam stabilizer. Can be used. Specific examples of the foam stabilizer (D21) include:
SH-193, SH-195 (manufactured by Toray Silicon Co., Ltd.),
SZ-1627, SZ-1931, SZ-1923, S
Z-1932 (manufactured by Nippon Unicar Co., Ltd.) and the like, and preferred examples are SZ-1931, SZ-1923, and SZ-1932.
-1932. The amount of the optional foam stabilizer (D21) is usually not more than 3%, preferably 0.1 to 3%, based on the total weight of the composition for forming a polyurethane foam.
%, Especially 0.2 to 2%. For example, in the case of a mechanical froth foam, the foam stabilizer (D21) is 0.1%
In the case described above, the effect of minutely dispersing and holding the inert gas blown during the production of the foam is improved, and as a result, a molded article having a desired density and a desired cell diameter is easily obtained. If it is 3% or less, the foam stabilizer hardly bleeds out to the surface of the molded article.

As the urethanization catalyst (D22), amine catalysts (triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ', N'-
Tetramethylhexamethylenediamine, 1-isobutyl-2-methylimidazole, 1,8-diazabicyclo-
[5,4,0] -undecene-7) and metal catalysts (such as stannous octylate, dibutylstannic dilaurate, and lead octylate). The amount of the optional urethane-forming catalyst (D22) is usually not more than 5% based on the total mass of the polyurethane foam-forming composition,
Preferably 0.001 to 3.5%, especially 0.01 to 3%
It is. When the amount of the catalyst is 0.001% or more, the curing speed is increased, and the diameter of the cells in the molded article is not increased, so that the texture of the molded article is not coarse. The more the amount of the catalyst, the finer the texture of the foam tends to be. However, if it exceeds 5%, the curing may be too fast and the production of the foam may be hindered.

The inorganic powder (D23) is used for improving the dimensional stability and mechanical strength of the molded product or for imparting flame retardancy. The average particle size of the inorganic powder is preferably 50 μm or less, particularly preferably 10 μm or less, for the purpose of improving dimensional stability and mechanical strength. Specific examples of the inorganic powder (D23) include, for example, calcium carbonate, silica, kaolin, talc, aluminum hydroxide, calcium sulfate, barium sulfate, zinc white, titanium oxide, crushed stone, alumina, mica, fly ash, bentonite, ceramic Powder, milled fiber and the like. Preferred among these are calcium carbonate, aluminum hydroxide, silica and talc.

Since the hollow microspheres (D24) are in a hollow state, they are used as a factor for forming the foam layer, and are used for reducing the weight of the molded product and improving the processability. Examples of such hollow microspheres (D24) include hollow microspheres made of thermoplastic resins such as polyvinylidene chloride, polymethyl methacrylate, and polyacrylonitrile, and thermosetting resins such as phenolic resins, epoxy resins, and urea resins. And hollow microspheres made of inorganic substances such as glass, alumina, shirasu, and carbon. The diameter of the hollow microsphere (D24) is usually 10 to 200 μm on average.
m, bulk specific gravity is usually 0.01 to 0.5. Specific examples of the hollow microsphere (D24) include Matsumoto Microsphere F-80ED and MFL series (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), and phenolic microballoon BJO-093.
0 (manufactured by Union Carbide), Glass Bubbles K-1
5, K-37 (manufactured by Sumitomo 3M Limited) and the like.

The dehydrating agent (D25) is used when forming a mechanical froth foam or a syntactic foam, and becomes a foaming agent in the urethane-forming reaction when water or moisture is mixed in the foam-forming composition. This is used to prevent the occurrence of a crack and to make the surface dense when the obtained molded product is cut. As the dehydrating agent (D25), a compound having a commonly used dehydrating effect can be used, but a neutral or alkaline dehydrating agent having a particle size of 0.1 to 50 μm is preferable. Preferable specific examples of the dehydrating agent (D25) include calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride, molecular sieve and the like, and preferred ones are calcium sulfate (hemihydrate gypsum) and molecular sieve.

As the short fibers (D26), those conventionally used for reinforcing thermosetting resins can be used. The short fiber (D26) has, for example, an effect of improving the dimensional stability, bending strength, and flexural modulus of the molded product. In addition, among (D26), the inorganic ones also have the effect of imparting flame retardancy. As a material of such a short fiber (D26), inorganic short fiber (D261) such as glass fiber, ceramic fiber, carbon fiber, rock wool, natural fiber,
Fiber materials such as synthetic fibers are exemplified. Of these, glass fibers are preferable in terms of effectively reinforcing the resin. The thickness of the short fiber (D26) is preferably 1 to 10,000 denier, particularly 10 to 2,000 denier. The length of the short fibers (D26) is preferably 0.1 to 50 mm, particularly 0.5 to 20 mm.

If necessary, a chain transfer agent (D27) can be used. Examples of (D27) include alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.) and enol ethers described in JP-A-55-31880. Chain transfer agent (D
The amount of 27) is preferably 0.0001 to 10 parts by mass, more preferably 0.0005 to 1 part by mass, per 100 parts by mass of the total of (a) and (c).

The dust scattering reducing agent (D28) is added as needed in the case of a rigid polyurethane foam for cutting. When the dust scattering reducing agent (D28) is contained, there is an effect of making the dust generated when the foam is cut into the air difficult to fly in the air. Therefore, it is preferable to include (D28) as the density of the foam is reduced. . Examples of the dust scattering reducing agent (D28) include an esterified product and an etherified product in which both terminal hydroxyl groups of polyalkylene glycol are blocked with a fatty acid or a higher alcohol.
Here, examples of the polyalkylene glycol include a homopolymer of EO or PO, and a block or random copolymer composed of EO and PO. Preferably, a homopolymer of EO and a block copolymer composed of EO and PO are used. The molecular weight of polyalkylene glycol is polyethylene glycol (hereinafter abbreviated as PEG).
Is usually 200 to 1000, preferably 200 to 6
00, and in the case of polypropylene glycol (hereinafter abbreviated as PPG), it is usually 200 to 4000, preferably 2
In the case of a copolymer composed of EO and PO (hereinafter abbreviated as PEPG), it is usually 400 to 5,000, preferably 1,000 to 3,000. Examples of the fatty acid include a saturated or unsaturated fatty acid having 8 to 18 carbon atoms. Here, examples of the saturated fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid, and examples of the unsaturated fatty acid include oleic acid, linoleic acid, and linoleic acid. Preferably, lauric acid and oleic acid are used. Examples of the higher alcohol include a saturated or unsaturated alcohol having 8 to 18 carbon atoms. Here, examples of the saturated alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, and examples of the unsaturated alcohol include oleyl alcohol. Preferably, they are lauryl alcohol, stearyl alcohol and oleyl alcohol. The dust scattering reducer (D28) may be used alone, or two or more kinds may be used in combination. (D28) may be in a solid form, but is desirably in a liquid or paste form at 20 ° C. in order to enhance the dust scattering suppression effect. Two or more kinds of dust scattering reducing agents (D28) may be used in combination, and at least one of them may be in a liquid or paste form. Particularly preferred as the dust scattering reducer (D28) is P
EG (molecular weight 200-600) dilaurate and dioleate.

In an embodiment of the polyurethane foam of the present invention, (A) has an M value represented by the following formula [3] of 500:
Rigid polyurethane foam [I], which is a component satisfying the following requirements, may be mentioned. M = J / (K + L × 2-2) [3] [where J is the (number average) molecular weight of (A); K is the (average) number of active hydrogen-containing groups per molecule of (A); L
Represents the number of (average) addition-polymerizable functional groups per molecule of (A). The M value of (A) used in the form [I] is preferably 3
00 or less, more preferably 250 or less, particularly preferably 50 to 200. If the M value exceeds 500, the mechanical strength of the rigid foam decreases. Preferred as the compound (c) optionally used in the rigid polyurethane foam [I] is one composed of one or more polyols selected from polyether polyols, polyester polyols and low molecular weight polyols.
The average hydroxyl value of the compound (c) used in the foam [I] is preferably from 200 to 1,000, more preferably from 250 to 700, particularly preferably from 300 to 6
50. In the case of the foam [I], when the hydroxyl value of the compound (c) is 200 or more, the heat resistance and strength of the obtained foam are increased, and when it is 1000 or less, the molded article becomes too hard and brittle. And no scorch is generated in the foam due to the heat of reaction.

Further, as an embodiment of the rigid polyurethane foam [I], a foaming agent (D1) as an auxiliary agent (D);
If necessary, a rigid polyurethane foam [Ia] having a density of 5 to 900 kg / m ³ using a foam stabilizer (D21) and / or a urethanizing catalyst (D22) as an additive (D2) may be mentioned. The density of the foam [Ia] is preferably 10 to 500 kg / m ³ , particularly preferably 20 kg / m ³ .
２００200 kg / m ³ . A flame-retardant rigid polyurethane foam can be obtained by using the inorganic powder (D23) and / or the inorganic short fiber (D261) as the additive (D2) in the foam [Ia]. When (D23) and / or (D261) is used for imparting flame retardancy to a foam, the amount used is preferably 9 to 40%, particularly preferably 20 to 40%, based on the total mass of the foam-forming composition. ~ 35%. (D23) and / or (D26)
If 1) is 9% or more, the flame retardancy is improved, and if it is 40% or less, the mechanical strength of the foam does not decrease.

In another embodiment of the foam [I], the foaming agent (D1) is not used as the auxiliary agent (D), and the additive (D) is used.
2) Mechanical floss method using inorganic powder (D23) and / or hollow microspheres (D24), dehydrating agent (D25) and, if necessary, foam stabilizer (D21) and / or urethanizing catalyst (D22). A rigid polyurethane foam [Ib] obtained by performing a polyurethane forming reaction. In the case of the mechanical floss foaming method, the inorganic powder (D2
3) and / or hollow microspheres (D24) serve as a nucleating agent when the inert gas is dispersed into fine bubbles by mechanical stirring in the polyurethane foam-forming composition, and the bubbles are stably retained. Play a role. The density of the foam [Ib] is usually 100 to 1800 kg / m ³ , preferably 2
00 to 1200 kg / m ³ , particularly preferably 300 to 1
000 kg / m ³ . As a further embodiment of the foam [I], the auxiliary agent (D) does not use the blowing agent (D1), and the additive (D2) includes hollow microspheres (D24), a dehydrating agent (D25), and an inorganic material if necessary. Rigid polyurethane foam [Ic] obtained by forming a syntactic foam using powder (D23).

The density of the foam [Ic] is usually 100 to 1
800 kg / m ³ , preferably 200 to 1200 kg /
m ³ , particularly preferably 300 to 1000 kg / m ³ . The rigid polyurethane foams [Ib] and [Ic]
It has the advantages that it is lightweight, has no density distribution, has a dense surface even when it is cut, and has little decrease in mechanical properties even when the density is reduced.

In the foams [Ib] and [Ic], the inorganic powder (D23) and the hollow microspheres (D24) are used as fillers. The amount of the hollow microspheres should be selected according to the use of the foam, since the hollow microspheres help to reduce the weight of the molded article and the processability. For example, in order to increase the strength and dimensional stability of the foam, the amount of inorganic powder may be increased, and in order to obtain a molded article having a low density and easy to be cut, the amount of hollow microspheres may be increased. The amount of the filler composed of the inorganic powder (D23) and the hollow microspheres (D24) is usually 2 to 60%, particularly 5 to 40%, based on the total mass of the foam-forming composition. When the content is 2% or more, the effect of retaining bubbles generated by the mechanical froth foaming method is sufficient, and when the content is 50% or less, the viscosity of the foam-forming composition does not increase too much and the production is easy.

In the foams [Ib] and [Ic], a dehydrating agent (D25) is added to prevent foaming during the urethanization reaction due to moisture in the foam-forming composition such as moisture in the filler. Therefore, the amount should be increased or decreased according to the moisture content in the composition, and when the amount of the filler is large, the amount of the dehydrating agent (D25) also needs to be increased. The amount of the dehydrating agent (D25) is usually 0.5 to 8%, preferably 0.8 to 6%, based on the total mass of the foam-forming composition. If it is 0.5% or more, the foaming phenomenon does not occur during the curing reaction due to moisture absorption, and the texture of the obtained molded product becomes fine. Further, when the content is 8% or less, the cutting workability is good.

In the foams [Ib] and [Ic], a dust scattering reducing agent (D28) is optionally added. (D2
8) has the effect of reducing the amount of dust scattered during cutting of a molded product. The amount of dust scattered tends to increase as the molded article has a lower density. Therefore, it is desirable to increase the content of (D28). The amount of (D28) is usually 3 to 30%, preferably 5 to 20%, based on the total mass of the foam-forming composition. When it is 3% or more, the effect of reducing the amount of dust scattering is sufficient, and when it is 30% or less, the hardness and heat resistance of the molded product are not affected.

By cutting the forms [Ib] and [Ic] into a desired shape, a cut molded product can be obtained. Examples of the cutting method include hand processing using only a saw, a plane, and the like, and mechanical processing using an NC machine, a machining center (MC), or the like.

The foams [Ia] to [Ic] may be rigid polyurethane foams using short fibers (D26) as the additive (D2). Short fiber (D
By using 26), a rigid foam having high flexural strength and flexural modulus can be obtained. In particular, in the present invention, the compounds (a) and (b) having the effect of reducing the viscosity of the composition are contained in the component (A). It can be a fiber reinforced foam. For example, at the time of producing the mechanical froth foam [Ib], even if the amount of the short fiber used in the composition is increased, the viscosity of the composition does not become higher than before and the mechanical stirring can be sufficiently performed. And the resulting foam has high mechanical strength. Thus, it is possible to provide a mechanical floss foam that can be used for applications such as a mold material that is repeatedly used or where bending stress is applied. When the short fiber reinforced foam is used, the amount of the short fibers (D26) is usually not more than 50% by mass, preferably 10 to 5%, based on the total amount of the foam-forming composition.
0% by weight, especially 20 to 40%. If it is 10% or more, the reinforcing effect of the resin is increased, and if it is 50% or less, a uniform foam can be obtained without generating defects in the foam. When the foams [Ib] and [Ic] are short fiber reinforced foams, the short fibers (D26), the inorganic powder (D23), the hollow microspheres ( D
The total amount of 24) is usually not more than 60% by mass, preferably 10 to 60% by mass, especially 20 to 50% by mass, based on the total amount of the foam-forming composition. Short fiber (D26) as a component of the foams [Ib] and [Ic]
If it contains, there is no characteristic of the density distribution, light weight and excellent dimensional stability, even if it is cut, the surface is dense, and it has features such as high flexural strength and flexural modulus.
It can be a short fiber reinforced rigid polyurethane foam.

Rigid polyurethane foam [I] has high strength, good heat insulation, good flame retardancy, and particularly excellent dimensional stability, and can be widely used for applications taking advantage of these features. Examples of uses of the rigid polyurethane foam [I] include a heat insulating material for refrigerators, freezers, and constructions, shock absorbers, synthetic wood, structural materials, model materials, and the like.

Another embodiment of the polyurethane foam of the present invention is a flexible polyurethane foam having a density of 10 to 500 kg / m ³ , wherein (A) has an M value represented by the above formula [3] of 500. Flexible polyurethane foam [II], which is a component satisfying the above requirements, may be mentioned. The M value of (A) used for Form [II] is preferably 800 or more, more preferably 1000 or more, and particularly preferably 1100 to 15000. M value is 500
If it is less than 10, the flexibility of the flexible foam is insufficient. The density of the foam [II] is preferably 15
２００200 kg / m ³ , particularly preferably 20-100 kg
/ M ³ .

Examples of the embodiment of the flexible polyurethane foam [II] include a foaming agent (D1) as an auxiliary agent (D) and a foam stabilizer (D21) and / or an additive (D2) as necessary.
Alternatively, a flexible polyurethane foam using a urethanization catalyst (D22) can be used. Further, a flame-retardant flexible polyurethane foam can be obtained by using an inorganic powder (D23) and / or an inorganic short fiber (D261) as the additive (D2). The amount of (D23) and / or (D261) used is the same as in [Ia]. The flexible polyurethane foam [II] has advantages of high foam hardness, low density, and low compression set, and thus can be widely used for applications utilizing these features. Flexible polyurethane foam [I
Examples of the use of [I] include cushioning materials, shock absorbing materials, sound absorbing and absorbing materials, and automobile steering wheel materials.

An example of a method for producing a rigid polyurethane foam [Ia] by foaming a blowing agent of the present invention is as follows. First, a predetermined amount of the component (A) and, if necessary, at least one auxiliary agent (D) selected from the group consisting of a foaming agent (D1) and an additive (D2) are mixed. Then, using a polyurethane foaming machine or a stirrer, the mixture is rapidly mixed with the organic polyisocyanate (B) containing the polymerization initiator (C). ((C) may be mixed with (A). . ]. The obtained liquid mixture (foaming stock solution) is poured into a mold, cured for a predetermined time, and then demolded to obtain a rigid polyurethane foam. Further, a polyurethane foam can be obtained by spray foaming or continuous foaming. In the urethanization reaction, the one-shot method is preferable in the prepolymer method because the viscosity of the foaming stock solution obtained by mixing the components increases. The NCO index for producing the foam [Ia] is preferably 40 to 500, particularly preferably 60 to 500.
250. If the NCO index is less than 40, the calorific value during foaming is small, so that the foaming ratio may be small, the mechanical strength of the foam may be small, or the dimensional stability may be poor. On the other hand, if the NCO index exceeds 500, the foam may become brittle. In a usual urethane foam molding method, only (c) is used as a polyol component,
It is usually molded with an NCO index of 80 or more. This is NCO
This is because if the index is reduced, the mechanical strength decreases and the dimensional stability deteriorates. In the method of the present invention, by using the self-polymerizable (a) and / or (b), even if the NCO index is reduced, the crosslink density is higher than that of ordinary urethane foam, and the decrease in the mechanical strength of the foam is reduced. small. For this reason, even if only water is used as the blowing agent, the amount of the organic isocyanate with respect to the polyol does not increase, so that poor mixing hardly occurs during foaming.

An example of the method for producing the flexible polyurethane foam [II] by foaming the blowing agent of the present invention is as follows. First, a predetermined amount of the component (A) and, if necessary, at least one auxiliary agent (D) selected from the group consisting of a foaming agent (D1) and an additive (D2) are mixed. Then, using a polyurethane foaming machine or a stirrer, the mixture is rapidly mixed with the organic polyisocyanate (B) containing the polymerization initiator (C). ((C) may be mixed with (A). . ]. The obtained mixture (foaming stock solution) is poured into a mold, cured for a predetermined time, and then demolded to obtain a flexible polyurethane foam. In the urethanization reaction, in the prepolymer method, the viscosity of the foaming stock solution obtained by mixing the components increases,
The one-shot method is preferred. Form [II]
Is preferably 40 to 15
0, particularly preferably 60 to 120. When the NCO index is less than 40, the amount of heat generated during foaming is small, so that the foaming ratio may be small, the stability of cells in the foaming process may be poor, or the mechanical strength of the foam may be reduced.
On the other hand, when the NCO index exceeds 150, the stability of the cells during the foaming process may be poor, or the foam may become brittle. In a usual urethane foam molding method, only (c) is used as a polyol component, and NCO is used.
The index is usually formed at 80 or more. This is because when the NCO index is reduced, the mechanical strength is reduced, and the curing property at the time of demolding is deteriorated. In the method of the present invention, by using the self-polymerizable (a) and / or (b), even if the NCO index is reduced, the crosslink density is higher than that of ordinary urethane foam, and the decrease in the mechanical strength of the foam is reduced. small. For this reason, even if only water is used as the blowing agent, the amount of the organic isocyanate with respect to the polyol does not increase, so that poor mixing hardly occurs during foaming.

The mechanical floss foam of the present invention [I
b] or a syntactic foam [Ic] is formed as follows. The foam-forming composition is usually composed of a component (A) (hereinafter abbreviated as an active hydrogen component in the description of the present production method) and a component (B) of an organic polyisocyanate (hereinafter referred to as the present production method). In the explanation, it is abbreviated as NCO component).
It is manufactured in two components. In the production of the active hydrogen component and the NCO component, various raw materials are mixed using a mixing tank equipped with a stirring blade such as a propeller type or a paddle type, a planetary mixer, a Hobart mixer, or the like. Form [Ib],
In [Ic], fillers such as inorganic powder and hollow microspheres,
A dehydrating agent, a dust scattering reducing agent, a foam stabilizer, a urethanizing catalyst and the like are usually contained in the active hydrogen component, but may be contained in the NCO component. In particular, when the amount of the filler is large, it is preferable to include a part of the filler in the NCO component. in this case,
Depending on the amount of filler contained in the NCO component, the dehydrating agent
By adding to the CO component, it is possible to prevent the NCO component from changing with time (viscosity increase). Those used in small amounts, such as colorants and catalysts, may be added to the active hydrogen component in advance.However, when the active hydrogen component and the NCO component are mixed and cured and molded, they are added simultaneously to the mixer. Is also good. The polymerization initiator (C) comprises an active hydrogen component and NC
It may be mixed with any of the O components. Active hydrogen component, NC
The composition comprising the O component is subjected to a polyurethane-forming reaction together with the polymerization of the addition-polymerizable functional group in the absence of a foaming agent to form a foam, whereby the foams [Ib] and [I
c] is obtained. Note that the forms [Ib] and [I
c] is preferably 40 to
500, more preferably 60 to 250, particularly preferably 85 to 120. If the NCO index is less than 40, the mechanical strength of the foam may decrease, or the coefficient of linear expansion may increase. On the other hand, if the NCO index exceeds 500, the foam may be hard and brittle.

The following steps are given as examples of the production method of the present invention for the mechanical froth foam [Ib] in which an inert gas is mixed and the syntactic foam [Ic] in which no inert gas is mixed. In the case of mixing an inert gas: (1) An active hydrogen component and an NCO component are produced by the above method. (2) An active hydrogen component, an NCO component and an inert gas are
Mix uniformly at a fixed ratio, and pour the mixture into a mold. (3) After curing in a mold, the mold is released to obtain a mechanical froth foam [Ib]. Here, as a mixing method, a mechanical floss method, that is, a mixer having a high shearing force such as an Oaks mixer is used, which is suitable for uniformly mixing the active hydrogen component, the NCO component, and the inert gas. The mechanical floss method is a method suitable for continuously mixing a gas into a liquid component. As the inert gas to be mixed, it does not react with the active hydrogen component or the NCO component, and is -30 ° C under atmospheric pressure
And non-liquid gases. Preferably, air, nitrogen, and carbon dioxide are used. As the amount of the inert gas to be mixed, with respect to the sum of the volume of the inert gas and the total volume of the composition,
Usually, it is 10 to 70%, preferably 20 to 60%. When no inert gas is mixed: (1) An active hydrogen component and an NCO component are produced by the above method. (2) The active hydrogen component and the NCO component are uniformly mixed at a fixed ratio, and the mixture is poured into a mold. (3) Defoam under reduced pressure to remove air bubbles contained in the mixed solution in the mold. (4) After curing in a mold, the mold is released to obtain a syntactic foam [Ic]. Here, as a mixing method, stirring with a stirring blade such as a propeller type, a flat blade type, a curved blade type, a Faudler type, and a paddle type in a stirring tank, or a mixer such as a screw type, a kneader type, a universal type, or the like. Used. Usually, a screw type mixer or a kneader type mixer is used.

The method for producing a polyurethane foam of the present invention can be particularly preferably used for foams having a complicated shape by using a specific polymerization initiator. It is preferably used as a method for producing a cushion material, an automobile seat back material, or an automobile headrest material.

[0085]

The present invention will be further described with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

Example 1 (Production of rigid urethane foam) 100 parts of glycerin dimethacrylate (a-1), 1.5 parts of "Silicone SH-193" (manufactured by Toray Silicone Co., silicone-based foam stabilizer), 7 parts of water [Iron (II) sulfate heptahydrate 7.0 × 10 ⁻⁵ M, ethylenediaminetetraacetic acid disodium salt dihydrate 7.0 × 10 ⁻⁵ M, Rongalit 3.
0 × 10 ⁻⁴ M], 10 parts of “Phirol CEF” (manufactured by Akzo Japan Co., Ltd., organophosphorus flame retardant), and “U
cat-1000 "(San Apro Co., Ltd., amine catalyst)
2.0 parts were blended and the temperature was adjusted to 25 ° C.
Crude MDI containing 0.01 parts of cumene hydroperoxide ("Parkmill H" manufactured by NOF Corporation) whose temperature has been adjusted to 0 ° C.
(NCO 31.4%) 172.7 parts were added, and the mixture was stirred at 3000 rpm for 10 seconds at a homodisper (a stirrer manufactured by Tokushu Kika Co., Ltd.) for 10 seconds.
100 mm (width) x 50 (height) mm was poured into an aluminum mold, demolded after 10 minutes to obtain a rigid polyurethane foam.

Example 2 (Production of rigid urethane foam) A rigid polyurethane foam was obtained in the same manner as in Example 1 except that disodium ethylenediaminetetraacetate dihydrate was not used.

Example 3 (Production of rigid urethane foam) A rigid polyurethane foam was obtained in the same manner as in Example 1 except that Rongalite was not used.

Example 4 (Production of rigid urethane foam) Instead of cumene hydroperoxide, t-butyl hydroperoxide ("Perbutyl H-6" manufactured by NOF CORPORATION) was used.
9 "), and a rigid polyurethane foam was obtained in the same manner as in Example 1 except that iron (II) sulfate heptahydrate, ethylenediaminetetraacetic acid disodium salt dihydrate and Rongalite were not used.

Example 5 (Soft urethane foam) 72 parts of polyol (c-1) obtained by adding 72 mol of PO and then 16 mol of EO to 1 mol of glycerin, 8 parts of glycerin monomethacrylate (a-2), "TEDA L3
0.6 "(manufactured by Tosoh Corporation, amine catalyst)," TOYO
CAT ET ”(Tosoh Corp., amine catalyst) 0.2 part,
1 part of "Silicone SRX-253" (manufactured by Toray Silicone Co., Ltd., silicone-based foam stabilizer), 5.5 parts of water [iron (II) sulfate heptahydrate 7.0 × 10 ^-5 M, disodium ethylenediaminetetraacetate] Salt dihydrate 7.0 × 10 ⁻⁵ M and Rongalite 3.0 × 10 ⁻⁴ M].
TDI / crude MDI = 80/2 containing 0.01 part of cumene hydroperoxide (“Parkmill H” manufactured by NOF Corporation) which was adjusted to a temperature of 5 ° C. and adjusted to a temperature of 25 ° C.
After adding 50.4 parts (NCO index: 100) of 0% by mass (NCO: 35.5%) (NCO index: 100), the mixture was stirred for 10 seconds at 4000 rpm by a homodisper (a stirrer manufactured by Tokushu Kika Co., Ltd.), and the temperature was adjusted to 60 ° C. by 300 mm (length). × 300mm (width) × 100m
m (height) was poured into an aluminum mold and demolded after 10 minutes to obtain a flexible polyurethane foam.

Example 6 (Production of flexible urethane foam) A flexible polyurethane foam was obtained in the same manner as in Example 5 except that disodium ethylenediaminetetraacetate dihydrate was not used.

Example 7 (Production of flexible urethane foam) A flexible polyurethane foam was obtained in the same manner as in Example 5, except that Rongalite was not used.

Example 8 (Production of flexible urethane foam) Instead of cumene hydroperoxide, t-butyl hydroperoxide ("Perbutyl H-6" manufactured by NOF CORPORATION) was used.
9 "), and a flexible polyurethane foam was obtained in the same manner as in Example 5 except that iron (II) sulfate heptahydrate, ethylenediaminetetraacetic acid disodium salt dihydrate and Rongalite were not used.

Example 9 (Production of instrument panel) 80 parts of polyol (c-1) obtained by adding 72 mol of PO and then 16 mol of EO to 1 mol of glycerin, 20 parts of diethylene glycol monoacrylate (a-3), triethanol Amine 2 parts, triethylamine 0.5 parts “TO
YOCAT ET ”0.2 parts and water 2.5 parts [iron (II) sulfate heptahydrate 3.5 × 10 ⁻⁵ M, ethylenediaminetetraacetic acid disodium salt dihydrate 3.5 × 10 ⁻⁵ M, Rongalit 1.5 × 10 ^-4 M] was charged into a raw material tank of a high-pressure foaming machine, the temperature was adjusted to 25 ° C., and the mixture was heated to 25 ° C. with paramenthane hydroperoxide 0. 0.11 parts crude MDI (NCO28
%) 76.4 parts (NCO index 105) was subjected to collision mixing at 15 MPa, and a skin material and a core material were set in advance, and 40%
The resulting mixture was poured into an aluminum mold whose temperature was adjusted to ° C., and after 1 minute, the mold was removed to obtain an instrument panel. Also, an aluminum mold (200 × 20) was prepared by controlling the temperature of the above mixture at 40 ° C.
0 × 10 mm), and after 1 minute, it was demolded to obtain a foam sample for measuring physical properties.

Example 10 (Production of urethane foam for instrument panel) [0095] The same procedure as in Example 9 except that disodium ethylenediaminetetraacetic acid disodium salt dihydrate was used as in Example 9 to prepare an instrument panel A foam sample for measuring physical properties was obtained.

Example 11 (Production of urethane foam for instrument panel) An instrument panel and a foam sample for measuring physical properties were obtained in the same manner as in Example 9, except that Rongalite was used.

Example 12 (Production of urethane foam for instrument panel) Instead of paramenthane hydroperoxide, t-butyl hydroperoxide ("Perbutyl H" manufactured by NOF Corporation) was used.
-69 "), and without using iron (II) sulfate heptahydrate, ethylenediaminetetraacetic acid disodium salt dihydrate and Rongalit, in the same manner as in Example 9 except for using an instrument panel and physical properties measurement. A foam sample was obtained.

Example 13 (Production of steering wheel for automobile) 1 mol of glycerin, 72 mol of PO, and then 16 mol of EO
100 parts of polyol (b-1) to which glycerol is added
Monomethacrylate (a-2) 16 parts, TEDA
L33 "(manufactured by Tosoh Corporation, amine catalyst) 0.6 parts," TO
YOCAT ET "(Tosoh Corporation, amine catalyst) 0.2
Section, "Neostan U100" (made by Nitto Kasei Co., Ltd.
Medium) 0.1 part, water 0.4 part [iron (II) sulfate heptahydrate7.
0x10 ^-FiveM, disodium ethylenediaminetetraacetate
Dihydrate 7.0 × 10^-FiveM, Rongalite 3.0 × 10
^-FourM) is mixed with a raw material tank of a high-pressure foaming machine.
And then adjust the temperature to 40 ° C.
0.01 parts of adjusted paramenthane hydroperoxide
Urethane-modified MDI containing 21.5% NCO
Four parts (NCO index: 100) were impact-mixed at 15 MPa
And set the iron core in advance and adjusted the temperature to 55 ° C
Inject into aluminum mold, remove after 1.5 minutes,
Got a handle. In addition, the temperature of the above mixture was adjusted to 40 ° C.
Into aluminum mold (200 × 200 × 10mm)
After 1 minute, remove the mold and obtain a foam sample for measuring physical properties.
Was.

Example 14 (Production of steering wheel for automobile) Instead of paramenthane hydroperoxide, t-butyl hydroperoxide ("Perbutyl H" manufactured by NOF Corporation) was used.
-69 "), except that iron (II) sulfate heptahydrate, ethylenediaminetetraacetic acid disodium salt dihydrate and Rongalite were not used. A foam sample was obtained.

Comparative Example 1 (Production of rigid urethane foam) A rigid polyurethane foam was obtained in the same manner as in Example 1 except that disodium ethylenediaminetetraacetate dihydrate and Rongalite were not used.

Comparative Example 2 (Production of Flexible Urethane Foam) A flexible polyurethane foam was obtained in the same manner as in Example 5, except that ethylenediaminetetraacetic acid disodium salt dihydrate and Rongalite were not used.

Comparative Example 3 (Production of Urethane Foam for Instrument Panel) An instrument was prepared in the same manner as in Example 9 except that disodium ethylenediaminetetraacetate dihydrate and Rongalite were used. A panel and a foam sample for measuring physical properties were obtained.

Comparative Example 4 (Manufacture of a steering wheel for an automobile) The same procedure as in Example 13 was carried out except that disodium ethylenediaminetetraacetic acid dihydrate and Rongalit were used. A foam sample was obtained.

The test method for rigid urethane foam is JIS
A 9511. The test method of the flexible urethane foam was performed according to JIS K6401. The test method of the instrument panel and the handle of the automobile was performed according to JISK6301.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

According to the method for producing a polyurethane foam of the present invention, the polyurethane foam of the present invention having high mechanical strength can be obtained. In addition to this, when a hydrogen atom-containing halogenated hydrocarbon (alternative fluorocarbon) is used in combination with water as the blowing agent, or when water is used alone, the foam has higher mechanical strength and volume Gives rigid foams with low modulus. When a low-boiling hydrocarbon and water are used in combination as the blowing agent, the cells of the foam are more uniform than before. When water is used alone as a blowing agent, a flexible foam having a higher mechanical strength than conventional foams is provided. By using the polymerization initiator of the present invention, the curability is excellent even at a lower liquid temperature and a lower mold temperature than in the conventional art, and the production speed is dramatically improved. Due to the above effects, the rigid polyurethane foam obtained by the method of the present invention is useful as a heat insulating material for refrigerators, freezers, and building materials. It is extremely useful as a material, a material for a vehicle handle, a vehicle seat cushion material, a vehicle seat back material, or a vehicle headrest material.

Claims (11)

[Claims] 1. An addition-polymerizable active hydrogen component (A) comprising the following (A1) or (A2), and an organic polyisocyanate (B), and a peroxide (d) and a transition metal-containing compound (e). In the presence of a polymerization initiator (C1) comprising a chelating agent (f) and / or a reducing agent (g), in the presence or absence of an auxiliary (D), together with the polymerization of an addition-polymerizable functional group. A method for producing a polyurethane foam, comprising performing a forming reaction. (A1): Compound (a) having an active hydrogen-containing group and an addition polymerizable functional group (A) (A2): Compound (a) having an active hydrogen-containing group and an addition polymerizable functional group Two or more compounds selected from the group consisting of a compound (b) having no hydrogen-containing group and a compound (c) having an active hydrogen-containing group and having no addition-polymerizable functional group 2. The method for producing a polyurethane foam according to claim 1, wherein the peroxides (d) are hydroperoxides. 3. The transition metal-containing compound (e) is an inorganic acid salt or an organic acid salt of at least one metal selected from the group consisting of iron, cobalt, manganese, vanadium and cerium. Method for producing polyurethane foam. 4. The method for producing a polyurethane foam according to claim 1, wherein the chelating agent (f) is ethylenediaminetetraacetic acid. 5. The method according to claim 1, wherein the reducing agent (g) is a sulfite.
5. The method for producing a polyurethane foam according to any one of items 4 to 4. 6. A water-soluble hydroperoxide (d1) comprising an addition-polymerizable active hydrogen component (A) comprising the following (A1) or (A2) and an organic polyisocyanate (B).
A method for producing a polyurethane foam, comprising conducting a polyurethane-forming reaction together with the polymerization of an addition-polymerizable functional group in the presence of a polymerization initiator (C2) comprising, or in the presence or absence of an auxiliary (D). (A1): Compound (a) having an active hydrogen-containing group and an addition polymerizable functional group (A) (A2): Compound (a) having an active hydrogen-containing group and an addition polymerizable functional group Two or more compounds selected from the group consisting of a compound (b) having no hydrogen-containing group and a compound (c) having an active hydrogen-containing group and having no addition-polymerizable functional group 7. The method for producing a polyurethane foam according to claim 1, wherein (a) and (b) are compounds having a terminal olefin type group represented by the following general formula [1]. (However, in the formula, R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms.) 8. (a) and (b) are acryloyl,
The method for producing a polyurethane foam according to claim 7, which is a compound having at least one group selected from a methacryloyl group and an allyl ether group. 9. The method for producing a polyurethane foam according to claim 1, wherein the active hydrogen-containing groups (a) and (c) are a hydroxyl group and / or a mercapto group. 10. A polyurethane foam obtained by the production method according to claim 1. 11. An automobile shock absorbing material, an automobile handle material, an automobile seat cushion material, an automobile seat back material, or an automobile headrest material, comprising the polyurethane foam according to claim 10.