JPH0476014A - Preparation of modified polyol composition and polyurethane - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give difficultly agglomerating dispersed polymer particles when used in the production of a polyurethane by mixing a polyol with a polymer prepared by polymerizing a specified ethylenically unsaturated monomer in a polyol. CONSTITUTION:A crosslinking,ethylenically unsaturated monomer selected from among compounds of formulas I and II (wherein X1, X2 and X3 are each a group of formula III or IV; R is H or CH3; and A1 and A2 are each an organic group), divinylbenzene, divinylacetone, divinylpyridine and 2,6- dicyano-1,6-heptadiene is mixed with 0.1-10 wt.% monomer selected from among an aromatic hydrocarbon monomer, an unsaturated nitrile and a (meth)acrylic ester to obtain an ethylenically unsaturated monomer. This monomer is polymerized in the presence of a polyol of a hydroxyl value of 200 or below and a molecular weight of 2000-30000, desirably polyether polyol, to obtain the title composition comprising the volyol and 1-80-wt.% polymer obtained from the above monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to modified polyol composition J6 and a method for producing polyurethane.

[Prior Art] Conventionally, in the production of polyurethane, when producing urethane foam using an organic polyisocyanate and an active hydrogen atom-containing compound, styrene and A method is known in which a modified polyol obtained by copolymerizing acryloni I and lyle is used.

[Problem to be solved by the invention] However, in this polyurethane foam production method, when the ratio of acrylonitrile to styrene is high, scorch (burning inside the polyurethane foam) tends to occur, so in order to prevent scorch, the ratio of styrene is increased. Then, there is a problem that the copolymer of styrene and acrylonitrile dissolves in the unreacted monomer and aggregates, making the dispersibility unstable. As a result of repeated studies on modified polyols that can provide foam hardness without causing agglomeration of the dispersed polymer even when the temperature is increased, the present invention has been achieved.

That is, the present invention provides: a modified polyol composition consisting of a polyol (a) and a polymer (C) obtained by polymerizing an ethylenically unsaturated monomer (b) in situ in (a); As part of the unsaturated monomer (b), the general formula % formula % (1) (wherein, Xl, X2. X3 is CH2=C(R)
Co - or CH2=C(R)O-. R is H or a methyl group. A11A2 is an organic group. ), divinylbenzene, divinylacetone, divinylpyridine, and 2,6-dicyano 1,11
A modified polyol composition (A) characterized in that it uses a crosslinkable ethylenically unsaturated monomer (d) selected from the group consisting of i-hebutadiene; an organic polyisocyanate and an active hydrogen atom-containing compound; , a method for producing polyurethane by reacting in the presence of a catalyst and/or a blowing agent if necessary, characterized in that the above-mentioned modified polyol composition (A) is used as at least a part of the active hydrogen atom-containing compound. A method for producing polyurethane and a method for producing a polyurethane foam by reacting an organic polyisocyanate and a compound containing an active hydrogen atom with a blowing agent and/or a catalyst in the presence of a foam stabilizer if necessary. This is a method for producing a polyurethane foam, characterized in that the above modified polyol composition (A) is used as at least a part of the compound.

Compounds represented by general formulas (1) and (2) include di- or tri(meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tri(meth)acrylate of glycerin. ; Divinyl ethers such as ethylene glycol divinyl ether and diethylene glycol divinyl ether; Polyisocyanates [tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and NCO group-containing prepolymers (obtained by reaction of the above polyisocyanate with an active hydrogen atom-containing compound) ) j etc. and hydroxyethyl (meth)acrylate. When other crosslinkable ethylenically unsaturated monomers such as butadiene and isoprene are used, the dispersibility becomes unstable.

Monomers other than (d) in the ethylenically unsaturated monomer (b) include aromatic hydrocarbon monomers (b+), unsaturated nitriles (b2), and (meth)acrylic esters. (ba) is preferred.

Examples of (bl) include styrene and α-methylstyrene.

Examples of (b2) include acrylonitrile and (meth)acrylonitrile.

Examples of (b3) include (meth)acrylic acid alkyl esters (alkyl group has 1 to 30 carbon atoms), specifically methyl (meth)acrylate, methyl (meth)acrylate, nonyl (meth)acrylate, denyl ( Meta) acrylic l/-1・, undecyl (meth) acrylic 1 note,
Dodecyl (meth)acrylate, 1-lydenle (meth)acrylate, tetradenle (meth)-no'acrylate, pentadenle (meth)acrylate, hexadene (meth)acrylate-1-, octadecyl (meth)acrylic Ll-1, Eikonl ( Meta) acrylate, Doconl (meth) acrylate;＞ , 'l'L
Ru.

”2), and 1 other 114j (1+
4) can also be used conveniently. (b4) includes enosynthetic unsaturated carboxylic acids and their derivatives [(meth)acrylic acid, (meth)acrylamide IJ], I fatty acid hydrocarbon + 1. (1 body [ethylene, propylene, etc.], fluorine-containing vinyl monomer [perfluorooctylethyl methacrylate-1, perfluorooctylethyl acrylate], nitrogen-containing vinyl IL ff1
Examples include diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.

Polyfunctional ethylenically unsaturated monomer (d) in ethylenically unsaturated monomer (b), aromatic hydrocarbon monomers (b), unsaturated nitriles (b2), (meth)acrylic acid The amounts of the esters (b3) and other monomers (b4) can be varied depending on the required physical properties of the polyurethane.

The content of (b) is as follows: The content of (d) is usually 0.1 to IO weight percent, preferably 0
．． It is 3 to 8% by weight, more preferably 0.5 to 5% by weight.

If the content of (d) is less than 0.1, the solubility of the polymer (c) will not be improved, and if it exceeds 10%, it will gel.

The content of (bl) is usually 0 to 99.9% by weight, preferably 20 to 80% by weight.

The Bk content of (b2) is usually 0-99.5% by weight, preferably 40-85% by weight.

The content of (b3) is usually 0 to 50% by weight, preferably 0 to 50% by weight.
It is 20% by weight.

(b4) is usually 0 to 10% by weight, preferably 0 to 5% by weight. (b4) exceeds 10% by weight'i I
JJ becomes hard.

The ratio of (b+) and (b2) is usually 0:100~
+00:0, preferably O: 100-80:2
It is 0.

The polymer content is 1 to 80% by weight, preferably 20 to 7.
It is 0% by weight.

As the polyol (a) used in producing the modified polyol composition of the present invention, a polyether polyol can be used.

The polyether polyol is a compound having at least 2 (preferably 2 to 8) active 1<1 hydrogen atoms (for example, polyhydric alcohol, polyhydric phenol, amines, polycarboxylic acid, phosphoric acid, etc.) and alkylene. Compounds having a structure in which oxide is added and mixtures thereof can be mentioned.

Examples of the polyhydric alcohols include alesin glycol, diethylene glycol, pro-IrL non-glycol, 1.
3- and 1,4-butanediol, tohexanediol, neopentyl glycol, and cyclic alcohols (for example, those described in Japanese Patent Publication No. 45-1474) trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, triethanolamine; tetrahydric alcohols such as pentaerythritol, methylglycondo, diglycerin; and further Sugar alcohols with high functionality, such as adonitol, arabitol, xylitol, pentitol, sorbitol, mannitol, idylin, talitol, dulcitol; sugars, such as glucose, mannose, fructose. , sorbose and other monosaccharides, sucrose,
oligosaccharides such as crehalose, lactose, raffinose; glycosides of polyols (e.g. glycols such as ethylene glycol, propylene glycol, alkane polyols such as glycerin, trimethylolpropane, hexanetriol); polyalkane polyols such as triglycerin, tetra Polyglycerols such as glycerin. Examples thereof include polypentaerythritols such as dipentaerythritol and tripentaerythritol; and cycloalkane polyols such as tetrakis(hydroxymethyl)cyclohexanol.

The above-mentioned polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A1 and bisphenol sulfone; condensates of phenol and formaldehyde (novolak), for example, US Pat. No. 3211i
Examples include polyphenols described in No. 5Ei41.

Examples of amines include ammonia; alkanolamines such as mono-di and triethanolamine, isopropanolamine, and aminoethylethanolamine, and c2-CG alkylene diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, and polyalkylene polyamines such as diethylene triamine. , aliphatic amines such as tri-ethylenetetramine; aromatic amines such as aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine; isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, etc. Examples include alicyclic amines such as aminoethylpiperazine and other heterocyclic amines described in Japanese Patent Publication No. 55-21044.

Two or more of these active hydrogen atom-containing compounds may be used in combination. Among these, polyhydric alcohols are preferred.

Examples of the alkylene oxide to be added to the active hydrogen atom-containing compound include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO),
, 2-, 1,3-, 1,4-, 2,3-butylene oxide, styrene oxide, and combinations of two or more of these (block and/or random addition).

Among the polynityl polyols, those having a polyoxypropylene chain and those having a polyoxypropylene chain and a polyoxyethylene chain (EO content of 25% by weight or less) are preferred.

The above-mentioned polyether polyols include those obtained by adding PO to the above-mentioned active hydrogen atom-containing compound; and those obtained by adding PO and other alkylene oxide (hereinafter abbreviated as AO) in the order of 1) PO-AO (chipped). ,2
) Added in the order of PO-AO-PO-AO (balanced 3) Added in the order of AO-PO-AO, 4) Added in the order of PO-AO-PO (7) block adducts such as firn9'!J-); 5) landano and kikamono which are mixed additions of PO and AO;
and 6) those added in the order described in JP-A-57-209920; 7) random/blocks such as those added in the order described in JP-A-53-13700 (NJ Kamono, etc.) These may be used in combination.

As the polyol (a), polyether polyols are preferred, but other polyols may be used instead of or in conjunction with them. Other polyols include high molecular polyols (polyester polyols, polybutadiene polyols, acrylic polyols, etc.) and/or low molecular polyols as described below.

The hydroxyl value (average) of the polyol (a) is usually 200 or less, preferably 15-100, particularly preferably 20-100.
70 is not enough. If it exceeds 200, foaming is difficult.

The molecular weight of polyol (a) is usually 2,000 to 30,000
or more, preferably from 2,500 to 10,000. If the molecular weight is less than 2000, foaming is difficult. 30
If it exceeds 000, the viscosity of the resulting modified polyol composition increases.

The amount of the ethylenically unsaturated monomer (b) used in the production of the modified polyol composition (A) of the present invention is as follows:
The amount is usually 1 to 90 parts, preferably 5 to 60 parts, per 100 parts (parts by weight, hereinafter the same) of the total of ) and (b). (b
) exceeds 90 parts, separation of the polyol layer and polymer layer occurs. If it is less than 1 part, hardness will not be achieved.

The modified polyol composition (A) can be produced by a conventional method for producing a polymer polyol or a modified polyol. For example, in the polyol (1), the ethylenically unsaturated monomer (b) is polymerized in the presence of a polymeric compound (Rancal generator!), (U.S. 4).
R + Patent No. 33i1335+ Specification λ),'[Rokomei aq
-2,t'+:+7s;,'l! + Kosho 4 Komei 479!
113shi3, JP-A-50-15894 HJVr)
or a polymer obtained by prepolymerizing (1)) and 1+)i2
There is a method in which polymerization is carried out in the presence of a polymerization initiator such as a Rancal generator, and the former method is preferred.

Examples of the above polymerization initiators include those that initiate polymerization by forming 41 molecules, for example, 2,2--
Azobisisobutyroni 1~Ril (AIBN), Syn 1!
--7zobis(2,4-7 medylhaleronitrile)
(AVN) Nato azo compound; Nobenzoylpero;
1-Li 1', Ncumylperogizide, Bis(4-t
-buf-runku1cohequinle) peroxydicarbonate, -\n soil peroxide, lauroyl peroxide, and peroxide and JP-A-8L-7G517
Peroxides other than item 1 described in the above publication, persulfates, perborates, persuccinic acids, etc. can be used.

The amount of polymerization initiator used is usually 0.1-15%, preferably 0.2% based on the weight of the ethylenically unsaturated monomer (b).
~10%.

The above polymerization reaction can be carried out without a solvent, but it can also be carried out in the presence of an organic solvent (especially when the polymer concentration is high). Examples of organic solvents include benzene, toluene, xylene, ace-1-nitrile, ethyl acetate, hexane, heptane, dioxane, N,N-dimethylformamide, N,l+-dimethylacetamide, isopropyl alcohol, n-butanol, etc. It will be done.

If necessary, chain transfer agents such as alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, allyl alcohol, etc.), halogenated hydrocarbons (carbon tetrachloride, tetraodor Polymerization can be carried out in the presence of enol ethers described in JP-A No. 55-31880, etc.), and enol ethers described in JP-A No. 55-31880.

Polymerization can be carried out either batchwise or continuously. The polymerization reaction is performed using the amount of polymerization initiator: 111 ul
IDl or higher - 1 - Normally 60-180"Cp or higher or 9
0~160°CN 'Mr I stiffness 1' or 10
It can be carried out at a temperature of 0 to 150°C, and it can be carried out under a popular horse chestnut or even under reduced pressure.

After the completion of the polymerization reaction, the modified 141 polyol composition (A), which is t' and j, can be used as it is for producing polyurethane without any post-treatment, but after the completion of the reaction, the organic solvent and the decomposition products of the polymerization initiator are It is almost preferable to remove impurities such as unreacted monomers and unreacted monomers by conventional means.

Hydroxyl acid of modified polyol &+1 composition (8), ((111
It is usually 5 to 100, preferably 7 to 80, more preferably IO to 60.

In the method for producing polyurethane of the present invention, the modified 4-polyol ill composition (A) can be used in combination with other active hydrogen atom-containing compounds, if necessary. As other active hydrogen atom-containing compounds that may be used as necessary, other high-molecular polyols (B) and/or low-molecular active hydrogen atom-containing compounds (C), which are used in polyurethane production, can be used. .

As other polymeric polyols (B), polyether polyols, polyester polyols, and modified polyols can be used. Examples of the polyether polyol include those similar to the polyether polyols described in the section of raw material polyol (a) in (A) above.

As polyester polyols, dihydric alcohols such as the above-mentioned polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, ], 3- or 1,4-butanol, 1,6-hexanediol, neopendel glycol, or these together with glycerin, ester-forming derivatives such as polycarboxylic acids or their anhydrides and lower esters (e.g., adipic acid, sebacic acid, maleic anhydride, phthalic anhydride). , dimethyl terephthalate, etc.), or anhydrides thereof, and alkyleonoxides (EOlPO, etc.) are reacted (condensed), or lactones (such as ε-caprolactone) are subjected to ring-opening polymerization.

Examples of modified polyols include polyols obtained by polymerizing these polyols, polyether polyols, polyester polyols, etc.) and ethylenically unsaturated monomers (for example, JP-A-54-101899, JP-A-54-1223). !IG〢 published in the official gazette). Also used are polybutadiene polyols, vinyl polymers containing hydroxyl groups (acrylic polyols) such as those described in JP-A-58-57413 and 57414, natural oil-based polyols such as mustard oil, and modified polyols. can.

These polymer polyols (B) usually have 2 to 8, preferably 3 to 8 hydroxyl groups and 200 to 40,001 hydroxyl groups.
Preferably it has an OH equivalent of 400 to 3000.

Low-molecular active hydrogen atom-containing compounds (
G) at least 2 pieces (preferably 2 to 3 pieces,
A compound having a molecular weight of 500 or less (preferably 60 to 400), particularly preferably 2 active hydrogen atoms (hydroxyl group, amine group, mercapto group, etc., preferably hydroxyl group), such as a low-molecular polyol! 9-Amino alcohol can be used. Examples of low-molecular polyols include ethylene glycol, diethylene glycol, propylene glycol, cyfropylene glycol, l,4-butanediol, neopentyl glycol,
Dihydric alcohols such as hexanediol; chrycerin,
trimethylolpropane, pentaerythritol,
Trivalent or higher polyhydric alcohols such as zig□lyse phosphorus, α-methyl glucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose; low molecular weight (e.g. molecular weight 200
~400) polyhydric alcohol alkylene oxide adducts (polyethylene glycol, polypropylene glycol, etc.); low molecular weight diols having a cyclic group [for example, those described in Japanese Patent Publication No. 45-1474 (propylene oxide adduct of bisphenol A, etc.)] ; 3rd or 4th class
class nitrogen atom-containing low-molecular polyols [for example, JP-A-54
-Those described in Publication No. 13011i99 (N-alkyl dialkanolamines such as N-methylgetanolamine, N-butylgetanolamine, etc., and their 4
trialkanolamines (triethanolamine, tripropaturamine, etc.); thiodiethylene glycol, etc. Examples of the amino alcohol include mono- or di-alkanolamines (eg, monoethanolamine, jetanolamine, monopropanolamine, etc.). Preferred among these are low-molecular polyols (especially diols), specifically ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and mixtures of two or more of these. It is.

Preferred among these other active hydrogen atom-containing compounds are polyether polyols.

In the entire active hydrogen atom-containing compound [(A) and optionally (B) and/or (C), Di of (A) is usually 5% by weight or more, preferably 10 to 80% by weight. There is a difference. If (A) is less than 5% ff, the foam will not have hardness.

The amount of other polymeric polyol (B) is usually θ ~ 95% by weight
The weight is preferably 0 to 80% by weight. When (R) exceeds 95 weight, the foam has no hardness.

The amount of the low-molecular active hydrogen-containing compound (C) is usually 0 to 30% by weight, preferably 0 to 10% by weight. (C) is 30
If the amount exceeds % by weight, the exothermic temperature during the reaction becomes high and scorch occurs.

As the organic polyisocyanate used in the present invention, those conventionally used in polyurethane production can be used. As such polyisocyanate,
Aromatic polyisocyanates having 6 to 20 carbon atoms (excluding the carbon in the NGO group) (e.g. 2.4- and/or
, 6-tolylene diisocyanate (TDI), crude TD
11.2.4-- and/or 4.4--diphenylmethane diisocyanate) (MDI), crude MDI [:
Crude diaminophenylmethane (condensation product of formaldehyde and aromatic amine (aniline) or mixtures thereof: diaminodiphenylmethane and a small amount (e.g. 5
~20% by weight)' (mixture with trifunctional or higher functional polyamine) phosgenated product: polyallyl polyisocyanate (P
aliphatic polyisocyanates having 2 to 8 carbon atoms (e.g. hexamethylenedi, fsonane-1,
alicyclic polyisocyanate having 4 to 15 carbon atoms: f, -1. number 8 to I5
・nato); and modified 1d of these polyisonoanates
substances (urethane group, carbodiimide group, allophanate)
1(, ureano. (, pureeso h ) 1(, ureto/
O/), (, uretone imino, (, isocyanurate-1
・、! 1111. ．． l-1-ly-zolidonno, (including modified products); and '1. A mixture of polyisono-l and these 2-1 and 2) described in No. 7G517 of No. 7G517 can be obtained. Preferred among these are the commercially readily available polyisoane-1, such as 2,4- and 2-
G-TD+, and mixtures of these isomers, crude TD1.4,4'- and 2.4-MDI, mixtures of these isomers, crude 1. PAPI, also called IDI, and these polyisoane-1.
Urethane group, carbodiimide group, A1 derived from
They are modified polyisocyanates containing a -donoane-1 group, a urea group, a biuret group, and an incyanure-1-2Z group.

In the present invention, when producing polyurethane, the isocyanate index I NGO/equivalence ratio of active hydrogen atom-containing groups ×
100] is usually 80 to +40, preferably 85 to +12
0, particularly preferably 95-115. It is also possible to incorporate polyisocyanurates into the polyurethane with an isocyanate index significantly higher than the stated range (for example 300 to +000 or higher).

In the present invention, in order to accelerate the reaction, catalyst openings commonly used in polyurethane reactions, such as amine-based M medium (+
- tertiary amines such as -lyethyleneamine and N-ethylmorpholine), tin-based catalysts (stannous octylate, dibutyltin dilaurate, etc.), and other metal catalysts (lead octylate, etc.). The amount of catalyst is based on the weight of the reaction mixture, for example from about 0.001 to about 5
% used.

Further, in the present invention, a blowing agent (for example, methylene chloride, monofluorotrichloromethane, water, etc.) can be used if necessary during the production of polyurethane. The amount of blowing agent used can vary depending on the desired density of the polyurethane.

In the present invention, a regulator can be used as at least part of other additives that can be used as necessary. Examples of foam stabilizers include Henri-Kohne surfactants (polysiloxane-polyoxy/alkylene copolymers).

Other additives that can be used in the present invention include ff
Known additives include retardants, reaction retarders, colorants, internal molding agents, anti-aging agents, antioxidants, plasticizers, bactericides, carbon black and other fillers.

Polyurethane can be manufactured using conventional methods. ζN+ can be obtained by a known method such as a semi-prepolymer method or a prepolymer method. Typical packaging equipment can be used for producing polyurethane. ;I! ! ! In the case of a solvent, a device such as a kneader or an extorter can be used. Various types of unfoamed or foamed polyurethanes can be produced in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using low or high pressure mechanical equipment.

Furthermore, polyurethane can also be produced by removing gas such as dissolved air in the raw materials or air mixed during mixing by a vacuum method before and after mixing the raw materials (especially before mixing the raw materials). The method of the present invention is useful in producing flexible mold forms and slab forms. Molding can also be carried out by the RIM (reaction injection molding) method.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Note that parts, percentages, and ratios represent parts by weight, percentages by mold, and weight ratios, respectively.

The composition of the raw materials used in the Examples and Comparative Examples is as follows.

(1) Polyol: Polyol ■: Glycerin and sucrose (30/70% by weight
A polyol with a hydroxyl value of 42 (EO content: 10%), which is obtained by adding PO to ) and then adding EO.

Polyol ■: A polyol with a hydroxyl value of 55, which is made by adding PO to glycerin.

(2) Monomer: 8N: Acrylonitrile, ST: Styrene.

DVB: Divinylbenzene EGDMA: Ethylene glycol di(meth)acrylate EO: Ethylene oxide PO: Propylene oxide (3) polymerization initiator: AIBN: Azobisisobutyronitrile.

(4) Polyisocyanate: TDI-80, TDI-1
(5) Catalyst: Catalyst A: DABCO33LV () 33% lietin diamine.

dipropylene glycol solution).

Catalyst B: Neostane U-28 (tin catalyst) [manufactured by Nitto Kasei Co., Ltd.] (6) Foam stabilizer: L-520 (polyether siloxane polymer) [manufactured by Nippon Unicar Co., Ltd.] Examples 1 to 3 and Comparative Example 1 Modified polyol ether with the composition and conditions listed in Table 1.
■ was synthesized.

Table 1 Table 2 Examples 4 to 7 Modified polyols V to ■ were synthesized under the conditions listed in Table 2.

Comparative Example 2 and Examples 8 to 10 Polyurethanes were produced using some of the modified polyols produced by the synthesis methods shown in Tables 1 and 2 and according to the foaming formulations shown in Table 3.

=30- Density (kg/m3): JISKG301 25%IL
D (kg/3]4cm2): JIs KG382
Tensile strength (kg/cm2): JIS KEi301
Tear strength (kg/cm): JIS KG301
Cutting elongation (%): JISKG301 impact elasticity (%)
: JISKS382 Compression set (%): JIS
G382 [Effects of the invention] The method for producing polyurethane of the present invention has the following advantages compared to conventional methods:
By crosslinking a dispersed polymer of a modified polyol, a foam with increased hardness can be produced.

Since the polyurethane foam obtained according to the present invention exhibits the effects as shown in =L, it is extremely suitable for use in interior furnishings such as automobile interior parts and furniture.

Claims (1)

[Claims] 1. A modified polyol composition comprising a polyol (a) and a polymer (c) obtained by polymerizing an ethylenically unsaturated monomer (b) in situ in (a), As part of the ethylenically unsaturated monomer (b), there are general formulas X1-A1-X2 (1) ▲ Numerical formulas, chemical formulas, tables, etc. (R)CO- or CH2=C(R)O-.R is H or a methyl group.A1 and A2 are organic groups), divinylbenzene, divinylacetone, divinylpyridine, and 2,6-dicyano-1,6-heptadiene. 2. Monomers other than (d) in the ethylenically unsaturated monomer (b) are selected from the group consisting of aromatic hydrocarbon monomers, unsaturated nitriles, and (meth)acrylic esters. The modified polyol composition according to claim 1, which is a monomer (
A). 3. A method for producing polyurethane by reacting an organic polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst and/or a blowing agent if necessary, as at least a part of the active hydrogen atom-containing compound, as claimed A method for producing polyurethane, which comprises using the modified polyol composition according to item 1 or 2. 5. A method for producing polyurethane foam by reacting an organic polyisocyanate and an active hydrogen atom-containing compound with a blowing agent and/or a catalyst, if necessary in the presence of a foam stabilizer, in which at least one of the active hydrogen atom-containing compounds is reacted. A method for producing polyurethane foam, characterized in that the modified polyol composition according to claim 1 or 2 is used as part of the modified polyol composition.