JP3350462B2 - Method for producing polymer polyol composition and polyurethane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer polyol composition and a method for producing a polyurethane using the same.

[0002]

2. Description of the Related Art Conventionally, as a means for obtaining a polymer polyol having a high polymer content and good dispersion stability, a part of the polyol is combined with a coupling agent (silicon-containing compound, trialkoxyalkane, dialkoxyalkane, etc.). A method of polymerizing a vinyl monomer in the presence of a modified polyol which has been reacted to have a high molecular weight (for example, Japanese Patent Publication No. 6-62841), and a method of polymerizing a vinyl monomer in the presence of a macromer containing a urethane bond ( For example, JP-A-61-1159
No. 19) is known.

[0003]

However, the above-mentioned method is obtained when a vinyl monomer having a high styrene content is polymerized in a polyol, particularly when the vinyl monomer is polymerized in a polyol having a molecular weight of less than 5000. There are problems such as poor dispersion stability and high viscosity of the polymer polyol, and when they are used to form urethane foam, there is a problem that the high elongation is low.

[0004]

Means for Solving the Problems The present inventors have developed a polymer polyol composition which has a low viscosity and good dispersion stability even with a high polymer content, and provides a foam having high hardness and high elongation. As a result of intensive studies, the present invention has been achieved.
That is, the present invention includes the following (1) to (3). (1) In the polyol (a-1), the following polymer particles (b)
A polymer polyol composition (A) in which 1) is dispersed in an amount of 30 to 60% by mass based on the total composition. Polymer particles (b1): having a particle size distribution of 0.01 to 100 μm, and the mode of the particle size distribution when 300 μm or less is divided into 64 by a laser diffraction / scattering type particle size distribution analyzer (volume basis:%) Is [p] and the difference (μm) between the maximum particle size and the minimum particle size is [q], and the polymer particles have [p] / [q] of 2 or less. (2) The following polymer particles (b) are contained in the polyol (a-1).
2) A polymer polyol composition (A) in which 30 to 60% by mass is dispersed with respect to the total composition. Polymer particles (b2): having a particle size distribution of 0.01 to 100 μm, and having a particle size distribution curve of a micron level (1.0 to
100 μm) and submicron level (0.01 to
Polymer particles having a peak in each of the regions (less than 1.0 μm). (3) In the method for producing a polyurethane by reacting a polyol and an organic polyisocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer as required, any one of the polymer polyol compositions described above as at least a part of the polyol ( A process for producing a polyurethane, characterized by using A).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol (a-1) used in the present invention includes compounds having at least 2 (preferably 2 to 8) active hydrogen atoms (polyhydric alcohols, polyphenols, amines). , Polycarboxylic acids, phosphoric acids, etc.) and compounds having a structure in which an alkylene oxide is polyadded, and mixtures thereof.

Examples of the polyhydric alcohol include alkylene glycols (ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) and cyclic groups. Dihydric alcohols such as diols (for example, those described in JP-B-45-1474); Trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol and triethanolamine; pentaerythritol, methylglycoside, diglycerin And tetrahydric alcohols such as; and alcohols having higher functional groups,
For example, pentitol (Adonitol, arabitol,
Xylitol, hexitol (sorbitol, mannitol, iditol, talitol, dulcitol, etc.), saccharides (sucrose, monosaccharides (glucose, mannose, fructose, sorbose, etc.), oligosaccharides (crehalose, lactose, raffinose, etc.), etc.]; glycosides [For example, glucoside of polyol (alkane polyol such as glycol, glycerin, trimethylolpropane, hexanetriol)]; polyalkane polyol [for example, polyglycerin such as triglycerin, tetraglycerin]; polypentaerythritol (dipentaerythritol, tripetaerythritol) And the like; cycloalkane polyols such as tetrakis (hydroxymethyl) cyclohexanol.

The polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenolsulfone; condensates of phenol and formaldehyde (novolak); US Pat.
Polyphenol described in the specification of JP-A No. 41 is exemplified.

The amines include ammonia; alkanolamines such as mono-, di- and triethanolamine, isopropanolamine and aminoethylethanolamine; alkyl having 1 to 20 carbon atoms such as methylamine, ethylamine and n-butylamine. Amines;
Aliphatic amines such as alkylene diamines having 2 to 6 carbon atoms [eg, ethylene diamine, propylene diamine, hexamethylene diamine], polyalkylene polyamines [eg, diethylene triamine, triethylene tetramine]; aniline, phenylenediamine, diaminotoluene, xylylenediamine; Aromatic amines such as methylene dianiline and diphenyl ether diamine; alicyclic amines such as isophorone diamine, cyclohexylene diamine and dicyclohexyl methane diamine; aminoethyl piperazine;
And the like.

[0009] Two or more of these active hydrogen atom-containing compounds may be used in combination. Among them, particularly preferred are polyhydric alcohols.

Examples of the alkylene oxide to be added to the active hydrogen atom-containing compound include ethylene oxide (EO), propylene oxide (PO), butylene oxide, styrene oxide and a combination of two or more of these (block and / or random addition). Is mentioned. Preferred among the polyether polyols are those having a polyoxypropylene chain and those having a polyoxypropylene chain and a polyoxyethylene chain (EO content is 25% by mass or less). Examples of the polyether polyol include those obtained by adding PO to the active hydrogen atom-containing compound; and those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO) in the following manner. PO-AO added in order (tip) PO-AO-PO-AO added (balanced) AO-PO-AO added PO-AO-PO added Block adducts such as those (active secondary) and random adducts obtained by mixing and adding PO and AO. These may be used in combination of two or more.

The polyol (a-1) in the present invention is preferably a polyether polyol, but other polyols can be used instead of or together with this. Examples of the other polyol include a high-molecular polyol (polyester polyol, polybutadiene polyol, acrylic polyol, and the like) and / or a low-molecular polyol described below. Polyol (a-
The hydroxyl value (average) of 1) is preferably 200 or less, more preferably 15 to 100, and particularly preferably 20 to 70.
It is. When the hydroxyl value is 200 or less, foaming can be performed more favorably. The weight average molecular weight of the polyol (a-1) is
Preferably 500 to 10000, more preferably 100
It is 0-8000, more preferably 1000-5000. When the weight average molecular weight is 500 or more, foaming can be performed more favorably, and when it is 10,000 or less, the viscosity of the obtained polyol composition is low and handling is easy.

The polymer polyol composition (A) in the present invention is a polymer fine particle (for example, polystyrene or polychlorinated polymer) obtained by (co) polymerizing a monomer described below by a usual method such as suspension polymerization or emulsion polymerization. Vinyl) dispersed in the polyol (a-1),
The copolymer may be a (co) polymerized monomer, and the latter is more preferable. Also, two or more polymer polyols containing polymer particles having different particle size distributions can be blended. When two or more kinds are blended, one or more kinds of polymer polyol compositions in which polymer particles having a peak in a micron level (1.0 to 100 μm) region are dispersed, and a submicron level (0.01 to 1. (Less than 0 μm)
And at least one polymer polyol composition in which polymer particles having a peak in the above region are dispersed. Here, (co) polymerization means homopolymerization or copolymerization, and the same description method will be used hereinafter.

In the present invention, the polymer particles [(b
1) or (b2)], the particle size distribution by a laser diffraction / scattering type particle size distribution analyzer (LA-700; manufactured by Horiba Ltd.) is usually 0.01 to 100 μm, preferably 0.0 to 100 μm.
1 to 50 μm. If the maximum particle size exceeds 100 μm, the polymer particles settle and separate.

The polymer particles in the polymer polyol composition (A) of the polymer of the present invention have a particle size distribution within the above-mentioned range, and have at least one of the following conditions (i) or (ii): One must be satisfied. (I) With a laser diffraction / scattering type particle size distribution analyzer,
The mode value of the particle size distribution when [300 μm or less is divided into 64 on a logarithmic axis] [the largest value:% of the ratio (volume basis) of the particles included in the range of each divided particle size distribution to all the particles] is [ p], when the difference (μm) between the maximum particle size and the minimum particle size is [q], polymer particles (b1) (p1 / [q] is 2 or less (preferably 1.5 or less) ( ii) With a laser diffraction / scattering type particle size distribution analyzer, a micron level (1.0 to 100 μm, preferably 1.5 to 100 μm)
20 μm) and submicron level (0.01 to 1.0 μm)
m, preferably from 0.1 to 0.8 μm) (b2) Polymer particles having peaks in each of the regions (i) and (ii) are not in the above ranges (i) and (ii). A finely packed structure cannot be obtained, the apparent volume of the polymer particles increases, the viscosity increases significantly, and handling becomes difficult.

In the case where the polymer particles are the above (b1), the standard deviation of the particle size distribution measured by the above apparatus is 0.8 μm or more, especially 0.1 μm, in terms of the viscosity of the polymer composition. It is preferably from 9 to 2 μm. Also, (b1)
In the case of (1), it is preferable to have a particle size distribution in both the micron level (1.0 to 100 μm) and the submicron level (0.01 to less than 1.0 μm). In this case,
In (b1) or (b2), the volume ratio of the micron-level particles to the submicron particles is preferably (30 to 95) :( 5 to 70), and more preferably (3 to 95).
5-93): (7-65), particularly preferably (40-9)
0): (10 to 60). When the volume ratio of the submicron particles is 5 or more, the viscosity of the polymer polyol composition does not increase, and the tear strength of the produced urethane foam does not decrease. When the volume ratio of the submicron particles is 70 or less, the viscosity of the composition does not increase and the handleability is good. Also, 2 to the total volume of (b1) or (b2)
The content of particles having a size of 0 μm or more is preferably 5% or less. When it is at most 5%, the sedimentation stability of the polymer particles will be good.

The polymer polyol composition (A) of the present invention
In the method of producing a monomer by a method of polymerizing a monomer in a polyol, it is preferable to use a radically polymerizable reactive dispersant (d) in order to obtain submicron particles.
As (d), for example, a polyol (a-
At least a part of the hydroxyl group of 2) is reacted with 0.5 to 0.8 mol of alkylene dihalide, preferably to 1 mol of (a-2), to obtain a high molecular weight. On the other hand, it can be produced by reacting preferably 0.5 to 1.5 mol of the vinyl group-containing compound (e) by a conventional method. In this case, it is desirable that a part of the hydroxyl groups in (a-2) be converted to an alcoholate of an alkali metal (for example, potassium or sodium) and then reacted. The alkali metal halide by-produced by the reaction may or may not be removed. The reaction temperature is preferably from 10 to 200C, more preferably from 50 to 150C. The reaction pressure is not particularly limited, but considering the boiling point of methylene dihalide or the like (particularly in the case of dichloromethane),
Preferably 0 to 20 atm, more preferably 0 to 10a
tm.

In the above reaction, a solvent may be used if necessary. When a solvent is used, a solvent that uniformly dissolves the reaction system (toluene, tetrahydrofuran, N, N dimethylformamide, etc.) is desirable. As a reaction vessel,
A reaction tank provided with a stirrer or a conventional various mixer may be used. Examples of ordinary various mixers include an extruder, a Brabender, a kneader, and a Banbury mixer.

As the polyol (a-2) constituting the reactive dispersant (d) in the present invention, those exemplified as the above (a-1) can be used, but those having 3 or more functional groups can be used. preferable. (A-2) and (a-1) may be the same or different.

The alkylene dihalide used for producing the reactive dispersant (d) is preferably methylene dihalide and / or ethylene dihalide. Examples of methylene dihalide include dichloromethane, dibromomethane, and the like, and particularly preferred is dichloromethane.
1,2-dichloroethane as ethylene dihalide,
Examples thereof include 1,2-dibromoethane, and particularly preferred is 1,2-dibromoethane.

The vinyl group-containing compound (e) used in the production of the reactive dispersant (d) is a vinyl group-containing compound having a hydroxyl-reactive functional group, and (meth) acrylic acid or a derivative thereof [glycidyl ( Meth) acrylate, and (anhydride) maleic acid. Of these, particularly preferred is glycidyl (meth) acrylate. Here, (meth) acrylic acid means acrylic acid or methacrylic acid, and the same description method will be used hereinafter.

The average number of functional groups of the reactive dispersant (d) is 4 to
6, and the weight average molecular weight of the polyol (a
-2) weight average molecular weight (preferable range is 500 to 10)
000), preferably 2 to 6 times, more preferably 2 to 4 times
It is twice. If it is at least 2 times, the dispersion stability of the polymer polyol (A) will be better, and if it is at most 6 times, the viscosity will be low. As a result, the viscosity of (A) will be low and the handling will be easy.

The viscosity of (d) at 25 ° C.
Preferably 600 to 10000 cps, more preferably 800 to 8000 cps, particularly preferably 1000 to 6 cps
000 cps. A sufficient dispersion stabilizing effect can be obtained at a molecular weight of about 600 cps or more. When the viscosity is not more than 10,000 cps, the viscosity of (A) is low and the handling is easy.

The polymer particles (b1) or (b2) in the present invention include polymer particles of a vinyl monomer (c),
Examples thereof include polyurea particles, polyester particles, and polyurethane particles, and polymer particles of the vinyl monomer (c) are preferable. Examples of the vinyl monomer (c) constituting the polymer particles (b1) or (b2) include an aromatic hydrocarbon monomer (c-2), an unsaturated nitrile (c-3), and (meth) Acrylic esters (c-4) and mixtures of two or more of these monofunctional vinyl monomers are preferred. (C-
Examples of 2) include styrene, α-methylstyrene, hydroxystyrene, chlorostyrene and the like. (C
As -3), acrylonitrile, methacrylonitrile and the like can be mentioned. (C-4) includes (meta)
Acrylic acid alkyl esters (alkyl group having 1 to 30 carbon atoms) [Specifically, methyl (meth) acrylate,
Butyl (meth) acrylate, 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, eicosyl (meth) acrylate,
Docosyl (meth) acrylate, etc.], hydroxypolyoxyalkylene ether [e.g.
1000] mono (meth) acrylates.

In addition to the above, other monomers (c-5) can be used if necessary. (C-5) includes ethylenically unsaturated carboxylic acids and derivatives thereof (such as (meth) acrylic acid and (meth) acrylamide), aliphatic hydrocarbon monomers [such as ethylene and propylene], and fluorine-containing vinyl monomers [Perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, etc.], nitrogen-containing vinyl monomers [diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.], vinyl-modified silicon, and the like.

(C-2), (c) in the vinyl monomer (c)
The mass ratio of (-3), (c-4), and (c-5) can be changed according to the required physical properties of the polyurethane and the like, and is not particularly limited. An example is as follows. (C-2): preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and particularly preferably 50 to 100% by mass.
mass%. (C-3): preferably 0 to 95% by mass, more preferably 20 to 80% by mass. (C-4): preferably 0 to 50% by mass, more preferably 0 to 20% by mass. (C-5): preferably 0 to 10% by mass, more preferably 0 to 5% by mass.

(C) as (c-2) and (c-3)
When (c-2) and (c-3) are used, the mass ratio of (c-2) to (c-3) is preferably (5:95) to (100: 0), more preferably (20:80) to (100: 0), particularly Preferably it is (50:50)-(100: 0).

In the production of the polymer polyol composition (A) of the present invention, a bifunctional or higher polyfunctional vinyl monomer (c-1) is used as at least a part of the vinyl monomer (c). , (A) can be further improved. Examples of (c-1) include divinylbenzene, ethylene di (meth) acrylate, polyoxyalkylene [for example, a molecular weight of 200 to 1,000] di (meth) acrylate, pentaerythritol triallyl ether, trimethylolpropane tri (meth) acrylate, and the like. No.

The amount of (c-1) is preferably from 0.01% to 5%, more preferably from 0.05% to 1%, based on the total mass of (c). Among the vinyl monomers (c) described above, particularly preferred are those in which the styrene in (c-2) is at least 50% by mass.

The production of the polymer polyol composition (A) of the present invention is preferably carried out in the presence of the reactive dispersant (d) in the same manner as in the usual method for producing a polymer polyol.
As a specific example of the polymerization method, a method of polymerizing a vinyl monomer (c) in a polyol (a-1) containing (d) in the presence of a polymerization initiator (for example, US Pat. No. 3,338,335)
No. 1, Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. Sho 4
7-47999 and JP-A-50-15894.

The polymer polyol composition (A) of the present invention
Is produced by polymerizing (c) in (a-1) containing (d), the amount of reactive dispersant (d) used to obtain submicron particles is (a- 1) to 60% by mass, preferably 2 to 3% by mass, based on the total amount of 1), (c) and (d), that is, the mass of (A) obtained.
0 mass%, particularly preferably 2 to 20 mass%. If the amount is less than 1% by mass, submicron particles cannot be obtained.
If it exceeds 0% by mass, the viscosity of (A) becomes high and handling becomes difficult.

In (A), the content of the polymer comprising (c), that is, (b1) or (b2) is usually 30 to 60% by mass, preferably 30 to 55% by mass, based on the mass of (A).
%, Particularly preferably 35 to 50% by weight. When the content of the polymer is less than 30% by mass, sufficient foam compression hardness cannot be obtained, and when it exceeds 60% by mass, the viscosity of (A) becomes high and handling becomes difficult. Accordingly, in the above polymerization reaction, the content of (c) with respect to the total amount of (a-1), (c), and (d) is also usually 30 to 60% by mass,
Preferably 30 to 55% by mass, particularly preferably 35 to 5%.
0% by mass. The content of (c) and (d) is out of the above range, for example, the mass of (c) is 5 with respect to the mass of (d).
If it is less than 0%, it is difficult to obtain polymer particles (b2) having a particle size distribution curve having peaks in a micron level region and a submicron level region in one step.

The polymerization initiator is of a type which generates free radicals to initiate polymerization, for example, 2,2'-
Azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-arbo) Nitrile), 2, 2 '
-Azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl)
Propionitrile], azo compounds such as 1,1′-azobis (1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate; Organic peroxides such as benzoyl peroxide, lauroyl peroxide, and persuccinic acid; and peroxides other than those described in JP-A-61-76517; inorganic peroxides such as persulfates and perborates; Can be used. These may be used in combination of two or more.

The amount of the polymerization initiator used is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 5% by mass, particularly preferably from 0 to 5% by mass, based on the mass of the vinyl monomer (c). 0.2 to 2.5% by mass. When the amount of the polymerization initiator used is 0.05% by mass or more, the polymerization rate of (c) becomes high, and the content of the polymer composed of (c) in the polymer polyol (A) becomes sufficient, and when the amount is 10% by mass or less. If so, the molecular weight of the polymer comprising (c) does not decrease, and sufficient foam compression hardness can be obtained.

The above polymerization reaction can be carried out without solvent, but can be carried out in the presence of an organic solvent if necessary (especially when the polymer concentration is high). As an organic solvent,
Aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octene, nonene, and decene; alcohol solvents such as isopropyl alcohol and n-butanol; acetonitrile, ethyl acetate, and dioxane , N, N-dimethylformamide, N, N-dimethylacetamide and the like. If necessary, a chain transfer agent [for example, alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, allyl alcohol, etc.), halogenated hydrocarbons (carbon tetrachloride, tetrabromide) , Chloroform, etc.), enol ethers described in JP-A-55-31880, etc.].

The polymerization can be carried out either batchwise or continuously. The polymerization reaction is at or above the decomposition temperature of the polymerization initiator, preferably 60 to 180 ° C, more preferably 90 to 160 ° C,
It is particularly preferably carried out at 100 to 150 ° C., and can be carried out under normal pressure or under pressure, and further under reduced pressure. Polymer polyol composition (A) thus obtained
May be directly used for the production of polyurethane without any post-treatment, but after the polymerization reaction, the organic solvent, decomposition products of the polymerization initiator, impurities such as unreacted monomers are removed by conventional means (for example, It is desirable to remove by stripping. The hydroxyl value of the polymer polyol composition (A) is preferably from 5 to 100, more preferably from 7 to 8
0, particularly preferably 10 to 50.

In the process for producing the polyurethane of the present invention obtained by reacting a polyol with an organic polyisocyanate,
The polymer polyol composition (A) is used as at least a part of the polyol, and (A) is particularly preferably used for producing a polyurethane foam. Also, (A)
Can be used in combination with other ordinary active hydrogen atom-containing compounds as necessary. As other active hydrogen atom-containing compounds, other high molecular polyols (B) and / or low molecular weight active hydrogen atom-containing compounds (C) commonly used in the production of polyurethane can be used.

As the other high molecular polyol (B), polyether polyol, polyester polyol, modified polyol and a mixture thereof can be used. Examples of the polyether polyol include those similar to the polyether polyol exemplified in the section of the raw material polyol (a-1) in the above (A). Examples of the polyester polyol include the above-mentioned polyhydric alcohols (eg, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; And a trivalent or higher alcohol such as glycerin or trimethylolpropane) and an ester-forming derivative such as polycarboxylic acid or its anhydride or lower ester (eg, adipic acid, sebacic acid, maleic anhydride, anhydride). Condensation products with phthalic acid, dimethyl terephthalate, etc .; alkylene oxide (EO, PO, etc.) addition reactants; and products obtained by ring-opening polymerization of lactones (ε-caprolactone, etc.). . As modified polyols, polyols obtained by polymerizing these polyols (such as polyether polyols and / or polyester polyols) and ethylenically unsaturated monomers (JP-A-54-1018)
No. 99, JP-A-54-122396, etc.). In addition, polydiene polyols (such as polybutadiene polyol) and hydroxyl-containing vinyl polymers (acrylic polyols) (for example,
-57413 and JP-A-58-57414) and natural oil-based polyols such as castor oil.
The modified polyol can also be used. These other polymer polyols (B) preferably have 2 to 8, more preferably 3 to 8 hydroxyl groups, and preferably have 200 to 40 hydroxyl groups.
00, more preferably 400 to 3000 OH equivalents. Particularly preferred as (B) is a polyether polyol.

As the low molecular weight active hydrogen atom-containing compound (C) to be used if necessary, at least two (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl group, amino group, mercapto group) Etc., preferably having a molecular weight of 500 or less (preferably 60 to 40)
Compounds of 0), for example, low molecular polyols and amino alcohols can be mentioned. As the low molecular polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-
Dihydric alcohols such as butanediol, neopentyl glycol and hexanediol; glycerin, trimethylolpropane, pentaerythritol, diglycerin,
trihydric or higher polyhydric alcohols such as α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, and sucrose; polyhydric alcohol alkylene oxide adducts of low molecular weight (for example, molecular weight of 200 to 400) ( Low molecular weight diols having a cyclic group (for example, those described in JP-B No. 45-1474 (propylene oxide adduct of bisphenol A)); containing a tertiary or quaternary nitrogen atom Low molecular weight polyols [for example, those described in JP-A-54-130699 (N-alkyldialkanolamines such as N-methyldiethanolamine, N-butyldiethanolamine and the like and quaternized products thereof); trialkanolamines (trialkanolamines) Ethanolamine, etc. tripropanolamine)]; thiodiethylene glycol, and the like. Amino alcohols include mono- or di-alkanolamines such as monoethanolamine,
Diethanolamine, monopropanolamine, etc.). Of these, low molecular polyols (particularly diols) are preferred, and specifically, ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,
A mixture of more than one species.

The amount of (A) in the entire active hydrogen atom-containing compound [(A) and, if necessary, (B) and / or (C)] in the process for producing the polyurethane of the present invention is preferably at least 5% by mass, more preferably Preferably at least 10% by mass,
It is particularly preferably at least 20% by mass. (A) quantity is 5
When the amount is not less than mass%, the compression hardness of the urethane foam is sufficient. The amount of (B) is
Preferably it is 0-95 mass%, more preferably 0-80 mass%. If (B) exceeds 95% by mass, foam hardness may not be obtained. Furthermore, the amount of (C) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass. When the amount of (C) exceeds 30% by mass, the exothermic temperature during the reaction increases, and scorch may occur.

As the organic polyisocyanate used in the process for producing the polyurethane of the present invention, the usual ones conventionally used for producing polyurethane can be used. Examples of such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group) and crude products thereof (for example, 2,4- and / or 2,6-tolylene diisocyanate (TD)
I), crude TDI, 2,4'- and / or 4,4 '
Diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminophenylmethane @ formaldehyde and an aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount (for example, 5 to 20 mass%) of a trifunctional or higher polyamine A phosgenated product of a mixture thereof: polyallyl polyisocyanate (PAPI), etc.]); aliphatic polyisocyanate having 2 to 18 carbon atoms (for example, hexamethylene diisocyanate, lysine diisocyanate, etc.);
Alicyclic polyisocyanates (e.g., isophorone diisocyanate, dicyclohexylmethane diisocyanate); araliphatic polyisocyanates having 8 to 15 carbon atoms (e.g., xylylene diisocyanate); and modified products of these polyisocyanates (urethane group, carbodiimide) Group, allophanate group, urea group,
Buret group, uretdione group, uretonimine group,
Modified products containing an isocyanurate group and an oxazolidone group); and polyisocyanates other than those described in JP-A-61-76517; and mixtures of two or more thereof. Preferred of these are:
Commercially available polyisocyanates such as 2,4- and 2,6-TDI, mixtures of isomers thereof, crude TDI, 4,4'- and 2,4'-MD
I, a mixture of these isomers, PAPI also referred to as crude MDI, and a modified polyisocyanate containing urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group derived from these polyisocyanates Kind. In the present invention, the isocyanate index [Equivalent ratio of NCO / active hydrogen atom-containing group × 100] in producing polyurethane.
Is preferably 80 to 140, more preferably 85 to 1
20, particularly preferably 95 to 115. It is also possible to introduce polyisocyanurate groups into the polyurethane with an isocyanate index significantly higher than the above range (for example 300 to 1000 or more).

In the production of polyurethane, in order to accelerate the reaction, catalysts usually used in polyurethane reactions [for example, amine catalysts (tertiary amines such as triethyleneamine and N-ethylmorpholine), tin catalysts (octylic acid) Stannous, dibutyltin dilaurate, and other metal catalysts (such as lead octylate)]. The amount of catalyst is preferably from 0.001 to 5% by weight, based on the weight of the reaction mixture. In the present invention, a foaming agent (for example, methylene chloride, monofluorotrichloromethane, water, etc.) can be used as needed in the production of polyurethane. The amount of the foaming agent can be arbitrarily changed depending on the desired density of the polyurethane.

In the present invention, a foam stabilizer can be used if necessary. Silicone surfactant (polysiloxane-polyoxyalkylene copolymer) as foam stabilizer
And the like. In the present invention, a flame retardant can be used if necessary. Examples of the flame retardant include melamines, phosphates, halogenated phosphates, and phosphazene derivatives. Other additives that can be used in the present invention include a reaction retarder, a colorant, an internal release agent,
Conventional additives such as antioxidants, antioxidants, plasticizers, disinfectants, carbon black and other fillers are included.

The polyurethane can be produced by a usual method, and can be carried out by a known method such as a one-shot method, a semi-prepolymer method, a prepolymer method and the like. For the production of polyurethane, a commonly used production apparatus can be used. When no solvent is used, for example, an apparatus such as a kneader or an extruder can be used.
The production of various non-foamed or foamed polyurethanes can be carried out in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using a low-pressure or high-pressure mechanical device. Further, before and after mixing the raw materials (particularly before mixing the raw materials), polyurethane can be produced by removing a gas such as dissolved air in the raw materials or air mixed during mixing by a vacuum method. The method of the present invention is particularly useful for making flexible molded and slab foams. It can also be applied to molding by the RIM (reaction injection molding) method.

[0044]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In the following, parts,%, and ratio indicate parts by mass, mass%, and mass ratio, respectively.

The compositions, symbols, etc. of the raw materials used in the examples and comparative examples are as follows. (1) Polyol: Polyol a1: a polyol having a weight average molecular weight of 3000 and a hydroxyl value of 55 obtained by adding PO to glycerin. Polyol a2: a polyol having a weight average molecular weight of 5,000 and a hydroxyl value of 34 obtained by adding PO to glycerin. Polyol a3: PO is added to glycerin and then E
O-added weight average molecular weight 7000, hydroxyl value 24
(EO content 14%).

(2) Modified Polyol Modified Polyol f1: As described in Reference Example 2 of JP-A-61-115919, a 2-L reaction vessel was charged with a polyol and 1 mol of hydroxyethyl acrylate, and toluene diisocyanate was added in an amount of 1 mol. About 80 moles
A modified polyol having a number of functional groups of 2, a weight average molecular weight of 5,000 and a viscosity of 25,000 cps, obtained by stirring at 4 ° C. for 4 hours.

(3) Vinyl monomer, etc .: St: styrene GMA: glycidyl methacrylate MDC: methylene dichloride

(4) Polymerization initiator: AVN: 2,2'-azobis (2,4-dimethylvaleronitrile) (5) Polyisocyanate: TDI-80 (manufactured by Nippon Polyurethane Industry Co., Ltd.) (6) Catalyst: Catalyst A: DABCO (diaminobicyclooctane) [manufactured by Nippon Emulsifier Co., Ltd.] Catalyst B: Neostan U-28 (tin catalyst) [manufactured by Nitto Kasei Co., Ltd.] MeONa: sodium methoxide (7) Foam stabilizer: F- 242T; polyether siloxane polymer [Shin-Etsu Silicone Co., Ltd.]

Production Examples 1 to 3 [Production of Reactive Dispersant (d) (Modified Polyol)] A 1 L capacity equipped with a temperature controller, a vacuum stirring blade, a dropping funnel, a decompression device, a Dimroth, a nitrogen inflow and an outflow outlet. In a four-necked flask, add 50 parts of polyol a1 under a nitrogen stream.
After adding 0 g, the mixture was dehydrated under reduced pressure at 120 ° C. and 1 Torr for 2 hours. Subsequently, the mixture was cooled to 50 ° C., 32 g of MeONa was added, and methanol was removed at 150 ° C. and 1 Torr for 6 hours. Thereafter, the mixture was cooled to 120 ° C., 40 g of methylene dichloride (MDC) was added dropwise, and the mixture was stirred for 3 to 6 hours. 60
After cooling at 8 ° C., 8 g of glycidyl methacrylate was added,
Stir for 1 hour. After cooling, the by-produced salt was removed by filtration to produce a reactive dispersant d1. According to the formulation shown in Table 1, reactive dispersants d2 and d3 were produced in the same manner. Table 1 shows the composition and properties of these raw materials.

[0050]

[Table 1]

Comparative Examples 1 to 5 and Examples 1 to 4 According to the compositions shown in Table 2, a 1-liter four-hole type equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth, a nitrogen inlet and an outlet. A 25% equivalent of the polyol a1 was placed in a neck flask, heated to 125 ° C. with stirring, and then the raw material liquid (remaining raw material mixed liquid) was continuously dropped by a dropping pump over 4 hours. Polymer polyols D1 to D5 and polymer polyols A1 to A3 of the present invention were synthesized. Further, unreacted monomers were stripped under reduced pressure. Also, comparative polymer polyol D
4 and D5 were mixed at a ratio of 1: 1 to obtain a polymer polyol A4 of the present invention. Table 2 shows their properties and the like. [Particle Ratio, Particle Top, Maximum Particle Size, Minimum Particle Size, Mode, and Method for Measuring Average Particle Size (Volume Basis)] The obtained polymer polyol has a laser light transmittance of 70 to 90%. Was diluted with a polyol a1, and measured with a particle size distribution analyzer (Laser diffraction / scattering type particle size analyzer LA-700; manufactured by Horiba, Ltd.). The mode is 300μ
m is the largest value (%) of the ratio (volume basis) of the particles included in the range of each divided particle size distribution to all the particles when divided by 64 on the logarithmic axis, and the average particle diameter (μm) Indicates the particle diameter corresponding to 50% of the cumulative distribution of the volume-based particle size distribution. [P] / [q] is [p] for the mode value and [q] for the difference (μm) between the maximum particle size and the minimum particle size.
Asking.

[0052]

[Table 2]

COMPARATIVE EXAMPLES 6-8 AND EXAMPLES 5-8 Comparative polymer polyols and some of the polymer polyols of the present invention obtained according to the formulations shown in Table 2 were used and foamed as shown in Table 3 A foamed polyurethane was produced according to the recipe. Table 3 shows the evaluation results of these foam properties.

[0054]

[Table 3]

The methods for evaluating the physical properties of the foam in Table 3 are as follows. Density (kg / m ³ ): JIS K6301 25% ILD (kg / 314 cm ² ): JIS K63
82 Tensile strength (kg / cm ² ): JIS K6301 Tear strength (kg / cm): JIS K6301 Cutting elongation (%): JIS K6301 Rebound resilience (%): JIS K 6382 Breathability (ft ³ / min): Dow Type flow meter method (specimen 5 × 5 × 2.5) Compression set (%): JIS K 6382

In Examples 1 to 8 using the polymer polyol composition of the present invention, the dispersion stability (viscosity, average particle size) and foam properties were all at least a certain level as compared with Comparative Examples 1 to 8. It turns out that it is favorable.

[0057]

Industrial Applicability The polymer polyol composition of the present invention has a higher polymer content than conventional ones, and has extremely good dispersion stability and low viscosity. Further, according to the method for producing the polyurethane of the present invention using the polymer polyol composition as an essential polyol component, it is possible to produce a good polyurethane foam having high hardness and compression set, as compared with the conventional method, The strength and elongation of the foam can also be improved. Due to the above effects, the polyurethane foam obtained by the production method of the present invention can be used for interior parts of automobiles,
It is extremely useful for furniture and other interior furnishings.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-2066643 (JP, A) JP-A-5-59134 (JP, A) JP-A-9-309937 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 71/02-71/03 C08G 18/48-18/50 C08L 25/08-25/14 C08L 73/04-75/16

Claims (10)

(57) [Claims] 1. A polymer polyol composition (A) comprising the following polymer particles (b1) dispersed in a polyol (a-1) in an amount of 30 to 60% by mass based on the total composition. Polymer particles (b1): having a particle size distribution of 0.01 to 100 μm, and the mode of the particle size distribution when 300 μm or less is divided into 64 by a laser diffraction / scattering type particle size distribution analyzer (volume basis:%) Is [p] and the difference (μm) between the maximum particle size and the minimum particle size is [q], and the polymer particles have [p] / [q] of 2 or less. 2. The standard deviation of the particle size distribution of (b1) is 0.8.
The polymer polyol composition (A) according to claim 1, which has a size of not less than μm. 3. A polymer polyol composition (A) in which the following polymer particles (b2) are dispersed in the polyol (a-1) in an amount of 30 to 60% by mass based on the total composition. Polymer particles (b2): having a particle size distribution of 0.01 to 100 μm, and having a particle size distribution curve of a micron level (1.0 to
100 μm) and submicron level (0.01 to
Polymer particles having a peak in each of the regions (less than 1.0 μm). 4. The composition according to claim 1, wherein the volume ratio of micron-level particles to submicron-level particles in (b1) or (b2) is (30-95) :( 5-70).
The polymer polyol composition (A) according to any one of the above. 5. 20 μm in (b1) or (b2)
The polymer polyol composition (A) according to any one of claims 1 to 4, wherein the content of the particles having a particle size of m or more is 5% or less based on the total volume of (b1) or (b2). 6. The method according to claim 1, wherein (b1) or (b2) is (a-1)
The polymer polyol composition (A) according to any one of claims 1 to 4, which is a polymer obtained by polymerizing a vinyl monomer (c) therein. 7. The polymer polyol composition (A) according to claim 6, wherein at least 50% by mass of the vinyl monomer (c) is styrene. 8. As a dispersion stabilizer for dispersing (b1) or (b2) in (a-1), 1 to 60% by mass, based on the mass of (A), of a reactive dispersant (d) is contained. The polymer polyol composition (A) according to claim 6 or 7, wherein the composition is formed. 9. A method in which (d) reacts at least a part of the hydroxyl groups of the polyol (a-2) with an alkylene dihalide to increase the molecular weight, and further reacts the reaction product with a vinyl group-containing compound (e). The polymer polyol composition (A) according to claim 8, which is a modified polyol containing a vinyl group. 10. A method for producing a polyurethane by reacting a polyol with an organic polyisocyanate, if necessary, in the presence of a catalyst, a foaming agent and a foam stabilizer, wherein at least a part of the polyol is used as the polyol. A method for producing a polyurethane, comprising using the polymer polyol composition (A) described in the above.