JPH01252620A - Polymer polyol composition and production of polyurethane by using the same - Google Patents

Abstract

PURPOSE:To make it possible to improve the elasticity and touch of a polyurethane, by using a polymer polyol formed by polymerizing a (meth)acrylate in a polyol as an active hydrogen compound. CONSTITUTION:9-30C alkyl (meth)acrylate or its mixture with methyl methacrylate, acrylonitride, styrene, a nitrogen-containing (meth)acrylate or the like is polymerized in a polyol such as a trifunctional polyol formed by the addition reaction of glycerol with propylene oxide and ethylene oxide to obtain a polymer polyol composition comprising a modified polyol which is a homogeneous dispersion of the formed polymer in the polyol. An active hydrogen compound containing at least part of this composition is reacted with an organic polyisocyanate in the presence of a catalyst, a blowing agent and additives to obtain a polyurethane.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a novel polymer polyol composition, more specifically, a method for polymerizing a specific ethylenically unsaturated monomer (hereinafter referred to as upper monomer) in a polyol. The present invention relates to a polymer polyol composition obtained by the method, and a method for producing polyurethane characterized by using this polymer polyol.

[Prior Art] Polymer polyols obtained by polymerizing low molecular weight monomers in polyols have been known as polymer polyol compositions used in the production of polyurethane.

[Problems to be Solved by the Invention] However, when polyurethane foam is molded using this polymer polyol, the resulting foam has increased hardness and poor elasticity.

[Means for Solving the Problems] The present inventors have conducted repeated studies to find a polymer polyol suitable for producing a polyurethane foam with excellent elasticity and soft texture, and as a result, the present invention has been achieved. That is, the present invention consists of a polymer of a polyol (i) and an ethylenically unsaturated monomer (ii) dispersed in the polyol, and by polymerizing the ethylenically unsaturated monomer in the polyol. In the polymer polyol composition to be produced, (11) (A) is represented by the following general formula % formula % (wherein R1 represents hydrogen or a methyl group, and % R2 represents an alkyl group having 9 to 30 carbon atoms). ) A polymer polyol composition (first invention) characterized by using a monomer represented by A combined polyol composition (second invention) and (ii) obtained by combining the monomer of (1) above with a monomer selected from the group consisting of acrylonitrile, styrenes, or nitrogen-containing (meth)acrylates. A method for producing polyurethane by reacting an organic polyisocyanate and an active hydrogen-containing compound in the presence of a catalyst, a blowing agent, and other additives, if necessary. A method for producing polyurethane (fourth invention) characterized in that the polymer polyol composition according to any one of the first to third inventions is used as at least a part of the atom-containing compound.

In the general formula (1), the alkyl group having 9 to 30 carbon atoms in R2 is a linear or side chain alkyl group such as nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, tocosyl group. etc. Among these, preferred are alkyl groups having 12 to 22 carbon atoms.

When the number of carbon atoms in R2 is 8 or less, the degree of reduction in impact resilience is large.

The monomer represented by general formula C1) is nonyl (meth)
Acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, Examples include eicosyl (meth)acrylate, tocosyl (meth)acrylate, and mixtures of two or more thereof.

Other monomers may be used together with the monomer represented by general formula (1) if necessary. Examples of this monomer include ethylenically unsaturated nitriles [(meth)acrylonitrile, etc.], ethylenically unsaturated carboxylic acids and their derivatives [
(meth)acrylic acid, (meth)acrylate, etc.], aliphatic hydrocarbon monomers [ethylene, propylene, carbon number 4
Co-aromatic hydrocarbon monomers such as ~20 α-olefins [
styrene, methylstyrene, etc.], and their vinyl monoffi forms (nitrostyrene, vinyl acetate, etc.). Among these, preferably methyl methacrylate,
Nitrogen-containing (meth)acrylates, acrylonitrile, styrenes and mixtures thereof, more preferably methyl methacrylate.

The content of the monomer of general formula (1) is usually 5% or more, preferably 30% or more, based on the weight of all monomers.

The polyol (i) used in the production of the polymer polyol composition in the present invention is a compound having at least 2 (preferably 2 to 8) active hydrogen atoms (such as polyhydric alcohols, polyhydric phenols, amines, Examples include compounds with a structure in which alkylene oxide is added to polycarboxylic acid, phosphoric acid, etc.) and mixtures thereof.

Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, l, 3- and! , 4-butanediol, l,6-hexanediol, alkylene glycols such as neopentyl glycol, and diols that grow cyclic groups (for example, those described in Japanese Patent Publication No. 45-1474).
iAlcohol Trihydric alcohols such as methylolpropane, trimethylolethane, hexanetriol, triethanolamine; pentaerythritol, methyl glycoside,
Tetrahydric alcohols such as diglycerin; and sugar alcohols with higher functional groups such as adonitol, arabitol, xylitol, bentitol, nlubitol, mannitol, iditol, talitol, dulcitol, etc.; sugars such as glucose.

monosaccharides such as mannose, fructose, and sorbose;
A sugar, clehalose. oligosaccharides such as lactose and raffinose; glycosides such as polyols (e.g. glycols such as ethylene glycol and propylene glycol, glycerin);

Glucosides of poly(alkane polyols) such as trimethylolpropane, hexanetriol, etc.; poly(alkane polyols) such as triglycerin.

Polyglycerols such as tetraglycerin. Examples 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 A and bisphenol sulfone; condensates of phenol and formaldehyde (novolak);
Examples include polyphenols described in Specification No. 1.

In addition, examples of amines include ammonia; mono-, di-, and triethanolamine, inpropaturamine,
Alkanolamines such as aminoethylethanolamine C1-C2 alkylamines + C2-C6 alkylene diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, polyalkylene polyamines such as diethylene triamine.

Aliphatic amines such as triethylenetetramine; aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline.

Diphenyl ether diamine and other aromatic amines; alicyclic amines such as inphorone diamine, cyclohexylene diamine, and dicyclohexylmethane diamine; aminoethyl piperazine and other special publications
Heterocyclic amines described in JP-A-21044 can be mentioned. 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),
1.2-, 1.3-, 1.4-, 2.3-
Examples include butylene oxide, styrene oxide, etc., and combinations thereof (block and/or random addition) of 2 m or more.

Among the polyols (i), preferred are those having a polyoxyethylene chain, that is, as alkylene oxides, EO and other alkylene oxides (hereinafter abbreviated as AO) [particularly PO, and PO and other AOs (butylene oxide, styrene oxide, etc.) are preferred. ) in small amounts (for example, 5
(% or less) when used together]. The polyoxyethylene chain content (abbreviated as CEO amount) is usually 5% (weight %, the same applies hereinafter) or more, preferably 7 to 50%, and more preferably 10 to 40%. When EOffi is used in the production of polyurethane with less than 5% droplets, the reactivity is low and the curing property and initial physical properties are low (and the compatibility with the reaction partner, inanate, is poor, making it impossible to react in a homogeneous system, resulting in an unsatisfactory result). No effect can be obtained.Also, if the ECI exceeds 500A, the curing property will improve, but the viscosity will be high (and the workability will be poor), and the temperature characteristics and water absorption properties will be poor, so it is not preferable. .

In addition, even if the EO amount is less than 5%, it may be combined with an EO amount of 56 parts or more, or if the EOfl is 50%.
Those exceeding 50% can also be used in combination with 50% or less so that the overall (average) EOfl falls within the above range.

The above polyol having a polyoxyethylene chain includes EO and AO in the above active hydrogen atom-containing compound,
(I) Added in the order of AO-EO (typhupd)
, (n) Added in the order of AO-EO-AO-EO (balanced), (III) EO-AO-EO
(■) Block adducts such as those added in the order of AO-EO-AO (active secondary); (■) Random adducts with mixed addition of EO and AO; and (■) Vl) Japanese Patent Publication No. 57-2099
Random/block adducts such as those added in the order described in JP-A No. 20, and (■) added in the order described in JP-A-53-13700, etc., can be mentioned.

Among these, preferred are those having terminal polyoxyethylene chains, especially (I) and (■). The amount of terminal EO is usually 5%, preferably 7% or more, and more preferably 7 to 30%.

The internal EO amount is usually 50% or less, preferably 10 to 409
It is A.

The primary hydroxyl group content of polyol (i) is usually 20%
or more, preferably 30% or more, more preferably 509A
More preferably, it is 60% or more.

The hydroxyl group ai (average) of polyol (i) is usually 200
Below, preferably it is 15-100. If it exceeds 200, the resulting polyurethane will have high rigidity and become brittle, which is not preferable.

Polyols (i) have different hydroxyl values [for example, those with 70 or less (usually 50% by weight or more) and those with 80-5
In addition, a small amount (for example, 20% by weight or less, particularly 5% by weight or less) of a low-molecular-weight polyol with a high 4I hydroxyl group (for example, a hydroxyl value of 700 or more) may be used in combination. [Low-molecular polyols used in combination include the above-mentioned polyhydric alcohols [listed as raw materials in (i)], and low-mole AO adducts of the above-mentioned polyhydric alcohols and amines. ] The molecular weight of polyol (i) is usually 2,000 to 30,000
or more preferably 3,000 to 25,000. If the molecular weight is lower than 2000, the resulting polyurethane will have poor moldability and a molded product with poor elasticity.
Undesirable.

In the present invention, the amount of ethylenically unsaturated monomer (ii) used in the production of the polymer polyol is
The amount is usually 1 to 50 parts, preferably 3 to 20 parts, per 100 parts (parts by weight, hereinafter the same) of the total of (11) and (11).
When (ii) exceeds 50 parts, separation of the polyether shoe and the polymer layer occurs. If the first part is unfinished, the rebound resilience is poor. The polymer polyol in the present invention can be produced by a conventional method for producing a polymer polyol. For example, a method of polymerizing ethylenically unsaturated monomer (ii) in polyol (i) in the presence of a polymerization initiator (radical generator, etc.) (U.S. Pat. No. 3,383,351, Japanese Patent Publication No. 39-2
No. 4737, Japanese Patent Publication No. 47-47999, Japanese Patent Publication No. 1977-
15894, etc.), and a method in which a polymer obtained by pre-polymerizing +D and (i) are graft-polymerized in the presence of a radical generator, and the former method is preferred.

A polymerization initiator is usually used in these polymerizations.

The polymerization initiator is one that generates free radicals to initiate polymerization, such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-7zobis(
Azo compounds such as 2°4-dimethylvaleronitrile (AVN); dibenzoyl peroxide, dicumyl peroxide, and other peroxides or persulfates described in Japanese Patent Application No. 199180/1983.

Although perborates, persuccinic acids, etc. can be used, azo compounds, particularly AIBN and AVN, are preferred from a practical standpoint. The amount of the polymerization initiator used is 0.1 to 10%, preferably O92 to 5%, based on the polymerization of the ethylenically unsaturated monomer.

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 moisture content is high). Examples of organic solvents include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexaheptane, dioxane, N, dimethylformamide, NJ-dimethylacetamide, isopropyl alcohol, n-butanol, and the like.

Furthermore, if necessary, polymerization can be carried out in the presence of a known chain transfer agent other than alkyl mercaptans (carbon tetrachloride, carbon tetrabromide, chloroform, enol ethers described in JP-A-55-31880, etc.). .

Polymerization can be carried out either batchwise or continuously. The polymerization reaction is carried out at a temperature higher than the decomposition temperature of the polymerization initiator, usually 60 to 180°C.
Preferably 90-160°C, particularly preferably 100-15°C
It can be carried out at 0°C, and it can also be carried out under atmospheric pressure, increased pressure, or even reduced pressure.

After the completion of the polymerization reaction, the obtained modified polyol can be used as is for producing polyurethane without any post-treatment. It is desirable to remove it by conventional means.The hydroxyl value of the polymer polyol is usually 1.
5-90 preferably 20-80 more preferably 20-7
It is 0.

In the method for producing polyurethane of the present invention, the polymer polyol (a) can be used in combination with other active hydrogen atom-containing compounds if necessary. In addition to (a), other active hydrogen atom-containing compounds which may be used as necessary are commonly used in polyurethane production. High molecular polyol (b) and/or low molecular active hydrogen atom-containing compound (
C) can be used.

Other polymer polyols that may be used in combination include:
Polyether polyols, polyester polyols, and other polymer polyols can be used. Examples of the polyether polyol include those mentioned above as the raw material polyether polyol (i) in (a). As the polyester polyol, the above polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, !, 3- or 1,4-butanediol I
2411i alcohols such as 116-hexanediol and neopentyl glycol or mixtures thereof with trihydric or higher alcohols such as glycerin and trimethylolpropane) and/or polyether polyols (the above-mentioned EO content of 5% or more and/or 5%
polycarboxylic acids or their anhydrides, ester-forming derivatives such as lower esters (e.g. adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.), or their anhydrides. and alkyleonoxide (EO, P
react (condensate) lactones (ε
-caprolactone, etc.) can be obtained by ring-opening polymerization. Other polymer polyols include these polyols, polyether polyols and/or polyester polyols, etc.) and ethylenically unsaturated monomers [mentioned as raw material (ii) in (a) above: acrylonitrile, styrene, etc.] Polyol obtained by polymerizing (for example, JP-A-54-101
No. 899 and those described in JP-A-54-1223911i).

In addition, polybutadiene polyol, hydroxyl base and vinyl polymer (acrylic polyol) such as JP-A-58-5
Natural oil-based polyols such as those described in No. 7413 and No. 57414, castor oil, and modified polyols can also be used. These polyols usually have 2 to 8 hydroxyl groups and an OH equivalent of 200 to 4,000, preferably 2 to 4,000.
It has four hydroxyl groups and an OH equivalent of 400 to 3,000. Among these, preferred are polyether polyols, and more preferred are polyether polyols with an EO chain content (0 to 5 EO chains arbitrarily distributed in the molecule).
0% by weight, and 0 to 30% by weight of EO chains are tipped at the end of the molecule).

Low-molecular active hydrogen atom-containing compounds (
C) has a molecular weight of 500 or less (preferably 60 to 400) and has at least 2 (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl group, amine group, mercapto group, etc., preferably hydroxyl group). ) compounds such as low molecular weight polyols and amino alcohols can be used. Examples of low-molecular polyols include 2ai alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, l,4-butanediol, neopentyl glycol, and hexanediol; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α - Trihydric or higher polyhydric alcohols such as methyl glufuside, sorbitol, xylift, mannitol, dipentaerythritol, glucose, fructose, sia sugar; low molecular weight (e.g. molecular weight 200-400) polyhydric alcohol AO adducts (polyethylene glycol) (fur, polypropylene glycol, etc.); low-molecular-weight diols containing a cyclic group [
For example, those described in Japanese Patent Publication No. 45-1474 (propylene oxide adduct of bisphenol A, etc.)]: tertiary or quaternary nitrogen atom-containing W low-molecular polyols [for example, those described in Japanese Patent Application Laid-open No. 13011i99/1989 ( N-alkyl dialkanolamines such as tomethylgetanolamine, dobutylgetanolamine, etc. and their quaternized products); trialkanolamines (triethanolamine, triproptoolamine, etc.); thiodiethylene glycol, etc. . Examples of the amino alcohol include mono- or di-alkanolamines (monoethanolamine, jetanolamine, motuprobanolamine, etc.). Preferred among these are low-molecular polyols (especially diols), specifically ethylene glycol, I,4-butanediol, neopentyl glycol, l,6-hexanediol, and mixtures of two or more of these. It is.

The amount of polymer polyol (a) in the entire active hydrogen atom-containing compound [(a) and optionally (b) and/or (C)] is usually 20% by weight or more.

Preferably 50% by weight or more of other polymer polyols (b
) is usually 0 to 70% by weight, preferably 0 to 50% by weight, and 1 in compound (C) is usually 0 to 3% by weight.
0% by weight, preferably 0-25% by weight. If (a) is 20% by weight ungrooved, the impact resilience will be poor. When (C) exceeds 30% by weight, the exothermic temperature during the reaction increases,
Blisters tend to occur near the injection port of the molded product, and the rigidity of the molded product obtained is too high, resulting in a brittle molded product that is not suitable for practical use. As the polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. Such a polyisocyanate has a carbon number (excluding carbon in the NGO group) of 6 to 20.
aromatic polyisocyanates (e.g. 2,4- and/or 2,G-) lylene diisocyanate (TDI
), crude TDI, 2.4'- and/or
4,4′-dipheni! Remethane diisocyanate (MD
I), Crude-1 [crude diaminophenylmethane (
A condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof: A phosgenate of a mixture of diaminodiphenylmethane and a small amount (e.g. 5 to 20% by weight) of a trifunctional or higher functional polyamine: Polyarylboriisocyanate) (PAPI) etc; carbon number 2-1
8 aliphatic polyisocyanate (e.g. hexamethylene diisocyanate, lysine diisocyanate, etc.)
; C4-C15 alicyclic polyisocyanates (e.g. inphorone diisocyanate, dicyclohexylmethane diisocyanate); C8-C15 aromatic aliphatic polyisocyanates (e.g. xylylene diisocyanate, etc.); and modified products of these polyisocyanates ( Urethane group, carbodiimide group, aron mononate group,
modified products containing urea group, biuret group, uretdione group, uretonimine group, incyanurate group, oxazolidone group, etc.); and polyisocyanates other than the above described in Japanese Patent Application No. 199180/1980; and two or more of these Mixtures may be mentioned. Among these, commercially readily available polyisocyanates, such as 2;

4- and 2, Ili-TDI, and mixtures of these isomers.

Coarse! TDI, 4.4'- and 2.4'-MDI,
and mixtures of these isomers, PAPI, also called crude-old, and modified polyins containing urethane groups, carbodiimide groups, allophanate groups, urea groups, beureft groups, and incyanurate groups derived from these polyisocyanates. They are cyanates.

In the present invention, the incyanate index [NGO/active hydrogen atom-containing group] equivalent ratio X 1001 is usually 80 to 1 20. Preferably 85-110. Particularly preferably, it is 95 to 108 (total number of active hydrogen-containing groups (hydroxyl group, amino group) other than wood carboxyl groups). In addition, the incyanate index is significantly higher than the above range (for example, 300 to 1.000).
(or higher) It is also possible to incorporate polyisocyanurates into the polyurethane.

In the present invention, in order to accelerate the reaction, catalysts commonly used in polyurethane reactions [for example, amine catalysts (tertiary amines such as triethylene amine and N-ethylmorpholine), tin catalysts (stannous octylate, dibutyl Other metal catalysts (such as lead octylate) can be used. The amount of catalyst may be, for example, from about 0.001 to about 5%, based on the weight of the reaction mixture.
used in small amounts.

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 depends on the desired density of the polyurethane (
For example, it can be changed by 0.01 to 1.4 g/C (3).

Other additives that can be used as necessary in the present invention include surfactants as emulsifiers and foam stabilizers, and silicone surfactants (polysiloxane-polyoxyalkylene copolymers) are particularly important.

Other additives that can be used in car inventions include flame retardants, reaction retardants, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, fungicides, carbon black and other fillers. Examples include additives.

A polyurethane molded article can be produced by a conventional method, and can be carried out by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method. Manufacturing equipment commonly used can be used for producing polyurethane. In the case of no solvent, a device such as a kneader or an extruder 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).

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

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

(1) Polyol A: PO4,7 in 32 parts of glycerin
Part 08.

Next, 1,200 parts of EO was added to hydroxyl value 28-3.
Functional polyol.

(2) Polyol B: A bifunctional polyol with a hydroxyl group ai of 28, in which 3.004 parts of Po and 920 parts of EO were added to 7B parts of propylene glycol.

(3) Polyol C: Pentaerythritol 13[i
Hydroxic acid to which 6,164 parts 9 of PO and 700 parts of EO were added! &Tetrafunctional polyol with a valency of 32.

(4) Polymer polyol I: In 90 parts of polyol A, about 130 parts of dodecyl methacrylate and 5 parts of tridecyl methacrylate were added using 0 parts of AIBNl as an initiator.
Hydroxyl value 2 obtained by polymerization at a temperature of ℃
5.2 polymer polyol.

(5) Polymer polyol ■: In a mixture of 43 parts of polyol A and 843 parts of polyol, 7 parts of tetradecyl methacrylate and 7 parts of pentadecyl methacrylate are polymerized at a temperature of about 130°C using 0 parts of AIBNl as an initiator. A polymer polyol with a hydroxyl group ai of 24.1 obtained by

(6) Polymer polyol ■: In 95 parts of polyol C, 2.5 parts of hexadecyl methacrylate and 2.5 parts of octadecyl methacrylate using 5 parts of AIB No. as an initiator.
A polymer polyol having a hydroxyl value of 30.4, obtained by polymerizing the following:

(7) Polymer polyol ■: Polymerizing 5 parts of eicosyl acrylate and 5 parts of tocosyl acrylate in a mixture of 45 parts of polyol A and 845 parts of polyol at a temperature of about 130°C using 0 parts of AIBNl as an initiator. A polymer polyol with a hydroxyl value of 25°2 obtained by

(8) In a mixture of 47.5 parts of polymer polyether polyol A and 847.5 parts of polyol, using 0 parts of AIBNl as an initiator, 1.25 parts of tetradecyl methacrylate and 1.25 parts of tride/l methacrylate) and methyl methacrylate. A polymer polyol having a hydroxyl group ai26J obtained by polymerizing 2.5 parts at a temperature of about 120°C.

(9) Polymer polyol component In 90 parts of polyol A, 265 parts of tetradecyl methacrylate, 2.5 parts of tridecyl methacrylate, and 5 parts of dimethylaminoethyl methacrylate are polymerized at a temperature of about 130°C using 1,0 parts of AIBN as an initiator. A polymer polyol with a hydroxyl value of 25.2 obtained by

(10) Polymer polyol ■: Polymer polyol with a hydroxyl value of 25.2 obtained by polymerizing 10 parts of acrylonitrile in 90 parts of polyol A at a temperature of about 130°C using 0 parts of AIBNl as an initiator. .

(11) Crosslinking agent: EG:゛ Ethylene glycol (12) Polyisocyanate Coronate Summer 050: Modified liquid MDI [manufactured by Nippon Polyurethane Co., Ltd.] (13) Catalyst DABCO33LY: ) 33% dipropylene glycol solution of lyethylenediamine (14) ) Foaming agent Frene 11:) Lichlorofluoromethane [manufactured by Daikin Industries, Ltd. (+5)! i Foaming agent S H-190: Polyether polysiloxane polymer [manufactured by TOMU Silicone Co., Ltd. fM Co5F-29 [i2]: Polyether polysiloxane polymer [manufactured by TOMU Silicone Co., Ltd.] (16) Black Toner: Carbon black, anti-aging agent (
A mixture of ultraviolet absorbers, antioxidants, heat resistance improvers, etc.) dispersed in polyether polyol.

Examples 1 to 8: Comparative Examples 1 to 4 According to the molding recipe shown in Table 1, a polyol component consisting of a polymer polyol, a crosslinking agent, and a catalyst and an incyanate component were each heated in a high-pressure foaming machine under the following molding conditions. After charging the raw material into a tank and dissolving a certain amount of nitrogen gas into the polyol component under high pressure, the mixture is mixed in a high-pressure foaming machine to a thickness of 5.
III x Width 400 Iris x Length 1000 - Temperature am
Polyurethane moldings were produced by pouring into closed molds.

[Molding conditions] High pressure foaming machine: Claus Muff 1 PU40/4G
Discharge amount: Approximately 500g/sec Discharge pressure: 140~1eOKg8/2 Injection time: Approximately 2.0 seconds~3. 0 seconds Raw material temperature: Polyol component 4o±2°C Incyanate component 40 parts 2°C Mold temperature: 40 parts 2°C Type time 2 60 seconds Table 2 shows the results of measuring the physical properties of the obtained polyurethane molded product.

The physical property measurement method is as follows.

Density (g/c 2): Buoyancy method tensile strength (Kg/c+s”): J
IS K-6301 growth rate (%):
JIS-[1301 tear strength (Kg/cm')
): JIS K-[1301 hardness
(Shiken A): ＾ST D-2240 impact resilience (%): J Is K-
8382 Table-1 Table-1 (continued) Table-1 (continued) Table-2 Table-2 (continued) Table-2 (continued) Examples 9 to ■: Comparative Examples 5 to 7 According to the molding recipe described in Table 3 , Under the following molding conditions, a polyol component consisting of a polymer polyol, a crosslinking agent, and a catalyst and an incyanate component were respectively charged into the raw material tank of a low-pressure foaming machine, and mixed with the low-pressure foaming machine to form a sheet with a thickness of 10
Polyurethane foam was produced by pouring into a closed mold measuring 30 cm x 30 cm x 30 am.

[Molding conditions] Low pressure foaming machine: MEG-E-24 Discharge amount = approx. 130 g/sec Injection time: approx. 3.0 seconds Raw material temperature: Polyol component 25±2'C
Iso7anate component 25±2°C Mold temperature = 60±2°C Mold opening time = 8 minutes Table 4 shows the results of measuring the physical properties of the obtained polyurethane foam.

The physical property measurement method is as follows.

Density (g/c■2): Actual size measurement method Tensile strength (Kg/am”): JIS K-
[1301 Growth rate (%): JI
S K-6301 tear strength (Kg/c 2)
: JIS K-fi30125%ILD (
kg/314cs2): JIS 163828
5%ILD (kg/314c■a):, Hs-6382 Resilience (%): JI
SK-6382 compression set (%):
JIS K-6382 Table-3 Table-3 (continued) Table-4 Table-4 (continued) [Effects of the invention] When a polyurethane molded article is manufactured using the polymer polyol composition of the present invention, the conventional molded article A product with excellent rebound resilience can be obtained compared to the above. Therefore, by using this polymer polyol, it is possible to produce polyurethane molded articles that are soft to the touch and have excellent elasticity.

Because of the above-mentioned effects, polyurethane molded products manufactured using the polymer polyol obtained by the present invention can be used for automotive parts such as steering wheels, seat cushions, crash pads, and bumpers, as well as furniture using elastomers. It is extremely useful for indoor furnishings, etc.

Procedure NejIi Masayama 1. Display of incident 1986 Patent Application No. 1713'84 2.5 Ming name 3. Person who makes corrections September 21, 1986 (No change in content)

Claims (1)

[Claims] 1. Consisting of a polymer of polyol (i) and ethylenically unsaturated monomer (ii) dispersed in the polyol, the ethylenically unsaturated monomer is polymerized in the polyol. In the polymer polyol composition produced by (
As for ii), (A) the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R_1 represents hydrogen or a methyl group, and R_2 represents an alkyl group having 9 to 30 carbon atoms.) A polymer polyol composition characterized by using a monomer represented by: 2. As (ii), a polymer polyol composition obtained by using the monomer of the above (1) in combination with methyl methacrylate. 3. A polymer polyol composition obtained by using, as (ii), the monomer of the above (1) in combination with a monomer selected from the group consisting of acrylonitrile, styrenes, or nitrogen-containing (meth)acrylates. 4. A patented method for producing polyurethane by reacting an organic polyisocyanate and an active hydrogen-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, as at least a part of the active hydrogen-containing compound. A method for producing polyurethane, comprising using the polymer polyol composition according to any one of claims 1 to 3.