JP2004263192A - Polymer polyol composition, producing method therefor, and producing method for polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymer polyol composition having good dispersion stability even if a polymer particle content is high. <P>SOLUTION: The polymer polyol composition is obtained by polymerizing an ethylenically unsaturated compound (b) in a dispersing medium comprising a polyol (A) or the (A) and a diluent (C), and a polymer particle (B) being dispersed in the dispersing medium, in the presence of the following reactive dispersant (D11). The reactive dispersant (D11) comprises (a) a substantially saturated polyol and an unsaturated polyol containing a nitrogen-containing bond to which (e) a mono-functional active hydrogen compound having at least one polymerizable unsaturated group is connected through a polyisocyanate (f), in which an average value of the ratio of the number of the unsaturated groups per the number of the nitrogen-containing bonds derived from NCO groups in one molecule of the dispersant (D11) is 0.1-0.4. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

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

A polymer composition or mixture obtained by polymerizing an ethylenically unsaturated compound in a polyol is generally called a polymer polyol, and is widely used as a raw material for polyurethane resins such as polyurethane foams and polyurethane elastomers.
To further increase the polymer particle content in the polymer polyol for the purpose of producing a polymer polyol that gives a high-quality polyurethane having higher hardness and elastic modulus, as a means for obtaining such a polymer polyol, a part of the polyol is coupled. A method in which a vinyl monomer is polymerized in the presence of a modified polyol having a high molecular weight by reacting with an agent (silicon-containing compound, tetrakisalkoxy orthoformate, trialkoxyalkane, dialkoxyalkane, etc.) (for example, see Patent Document 1) A method of polymerizing a vinyl monomer in the presence of a macromer containing a urethane bond (for example, see Patent Document 2) is known.
International Publication WO85 / 04891 JP-A-61-115919

  However, there are problems such as poor dispersion stability of the obtained polymer polyol composition, and difficulty in handling due to poor mixing with the isocyanate at the time of polyurethane resin molding, and dispersion stability even when the polymer particle content is high. It was difficult to obtain a polymer polyol composition having good properties.

  The present inventors have conducted intensive studies in order to solve the above problems, and as a result, by using a specific terminal ethylenically unsaturated group-containing compound and / or a specific reactive dispersant, high-quality polyurethane. The present invention has been found to provide a polymer polyol composition having good dispersion stability and good dispersion stability.

That is, the present invention is the following seven inventions.
[First invention] A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein (B) is It is formed by polymerizing an ethylenically unsaturated compound (b) in the presence or absence of a dispersant (D), and at least 5% by mass of (b) has a number average molecular weight of 160 to 490 and a solubility of A polymer polyol composition comprising a terminal ethylenically unsaturated group-containing compound (b1) having a parameter SP of 9.5 to 13.
[Second invention] A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium. A) A polymer polyol composition formed by polymerizing an ethylenically unsaturated compound (b) in the presence of 0.5 to 50 parts by mass of the following reactive dispersant (D1) based on 100 parts by mass.
Reactive dispersant (D1): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol.
[Third invention] A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium. A polymer polyol composition formed by polymerizing an ethylenically unsaturated compound (b) in the presence of a reactive dispersant (D11).
Reactive dispersant (D11): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). (D11) a dispersant comprising a nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4. .

[Fourth invention] Production of a polymer polyol composition in which an ethylenically unsaturated compound (b) is polymerized in a polyol (A) in the presence or absence of a dispersant (D) and / or a diluent (C). In the method, (b) containing 5% by mass or more of a terminal ethylenically unsaturated group-containing compound (b1) having a number average molecular weight of 160 to 490 and a solubility parameter SP of 9.5 to 13 is used. (1) A method comprising obtaining the polymer polyol composition of the present invention.
[Fifth invention] A polymer polyol composition for polymerizing an ethylenically unsaturated compound (b) in a polyol (A) in the presence of a dispersant (D), in the presence or absence of a diluent (C). In the production method, the following reactive dispersant (D1) is used as the dispersant (D) to obtain the polymer polyol composition of the second invention.
Reactive dispersant (D1): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol.
[Sixth invention] A polymer polyol composition for polymerizing an ethylenically unsaturated compound (b) in a polyol (A) in the presence of a dispersant (D), in the presence or absence of a diluent (C). In the production method, the following reactive dispersant (D11) is used as the dispersant (D) to obtain the polymer polyol composition of the third invention.
Reactive dispersant (D11): a substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). (D11) A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4.

  [Seventh invention] In a method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component and a polyisocyanate component in the presence or absence of a foaming agent, any one of the above-mentioned as at least a part of the polyol component A method for producing a polyurethane resin, comprising using a polymer polyol composition.

ADVANTAGE OF THE INVENTION According to the polymer polyol composition of this invention and its manufacturing method, even if the density | concentration of a polymer particle is made high compared with the conventional polymer polyol composition, the low viscosity and dispersion stability are obtained very favorable polymer polyol composition. be able to. Therefore, in the production of a polyurethane resin or the like, the working efficiency can be extremely improved.
In addition, the polyurethane resin produced by using the polymer polyol composition of the present invention as an essential component of the polyol has the same viscosity as the polymer polyol composition, particularly when the polymer is a polymer of a monomer composed of (b1). In comparison, the case of using the polymer polyol composition of the present invention has a much better 25% ILD (hardness) than the case of using the conventional one. In addition, when the polymer polyol composition of the present invention is used, the 25% ILD of the urethane resin, the air permeability, and the compression set are lower than when the conventional polymer polyol composition having the same polymer particle concentration is used. It can be greatly improved.
Further, the polymer polyol compositions of the second and third inventions have extremely good dispersion stability as compared with those of the prior art, even when the polymer is a polymer composed of only monomers that are usually used. Polyurethane resin having high hardness and excellent wet heat compression set as compared with the method according to the above method can be produced.

In the present invention, as the polyol (A), a known polyol usually used for producing a polymer polyol can be used. For example, a compound having a structure in which an alkylene oxide is added to a compound containing at least two (preferably 2 to 8) active hydrogens (polyhydric alcohol, polyhydric phenol, amines, polycarboxylic acid, phosphoric acid, etc.) ( A1) and mixtures thereof.
Among these, preferred are compounds having a structure in which an alkylene oxide is added to a polyhydric alcohol.

  Examples of the polyhydric alcohol include dihydric alcohols having 2 to 20 carbon atoms (eg, aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). Alkylene glycols such as cycloaliphatic diols such as cyclohexanediol and cyclohexanedimethanol), and trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylolpropane, and trimethylol). Alkanetriols such as ethane and hexanetriol); polyhydric alcohols having 4 to 8 or more carbon atoms having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, alkane polyols and their intramolecular or intermolecular dehydration products, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.

  Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenolsulfone; and condensates (novolak) of phenol and formaldehyde.

Examples of the amines include ammonia; and examples of the aliphatic amines include alkanolamines having 2 to 20 carbon atoms (eg, monoethanolamine, diethanolamine, isopropanolamine, and aminoethylethanolamine), and alkylamines having 1 to 20 carbon atoms ( For example, n-butylamine and octylamine), alkylene diamine having 2 to 6 carbon atoms (eg, ethylene diamine, propylene diamine and hexamethylene diamine), polyalkylene polyamines (dialkylene triamine having 2 to 6 carbon atoms in the alkylene group) Hexaalkyleneheptamines, such as diethylenetriamine and triethylenetetramine).
An aromatic mono- or polyamine having 6 to 20 carbon atoms (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); an alicyclic ring having 4 to 20 carbon atoms Formula amines (isophorone diamine, cyclohexylene diamine and dicyclohexyl methane diamine); heterocyclic amines having 4 to 20 carbon atoms (for example, aminoethylpiperazine) and the like.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid, Isophthalic acid), and mixtures of two or more of these.

  The alkylene oxide to be added to the active hydrogen-containing compound is preferably one having 2 to 8 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), and 1,2-. , 1,3-, 1,4- and 2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide (hereinafter abbreviated as SO) and the like, and combinations of two or more of these (block and And / or random addition). Preferably, it is PO or a combination of PO and EO (EO content is 25% by mass or less).

Specific examples of the polyol include those obtained by adding PO to the above active hydrogen-containing compound, those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO) in the following manner, or the addition of these. Esterified products of a compound and a polycarboxylic acid or phosphoric acid are exemplified.
[1] Blocks added in order of PO-AO (tiped)
[2] Blocks added in the order of PO-AO-PO-AO (balanced)
[3] Blocks added in the order of AO-PO-AO [4] Blocks added in the order of PO-AO-PO (active secondary)
[5] Random addition product obtained by mixing and adding PO and AO [6] Random addition or block addition in the order described in U.S. Pat. No. 4,226,756 The hydroxyl equivalent of (A1) is preferably 200 to 4,000. And more preferably 400 to 3,000. It is also preferable that two or more (A1) are used in combination and the hydroxyl equivalent is within this range.

As the polyol (A), another polyol (A2) can be used in combination with the compound (A1) having a structure in which an alkylene oxide is added to the active hydrogen-containing compound. In this case, the use ratio (mass ratio) of (A1) / (A2) is preferably 100/0 to 80/20.
Examples of the other polyol (A2) include polymer polyols such as polyester polyols and diene-based polyols, and mixtures thereof.

  Examples of the polyester polyol include the above-mentioned polyhydric alcohols and / or polyether polyols [ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like. Polyhydric alcohols or mixtures of these with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane, and adducts of these polyhydric alcohols with low moles (1 to 10 moles) of alkylene oxides] Or an anhydride thereof, an ester-forming derivative such as a lower alkyl (alkyl group having 1 to 4 carbon atoms) ester (eg, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.); Carboxylic anhydride Reaction product of alkylene oxide (EO, PO, etc.) with a polylactone polyol, for example, ring-opening polymerization of a lactone (ε-caprolactone, etc.) using the above polyhydric alcohol as an initiator. And polycarbonate polyols, for example, a reaction product of the polyhydric alcohol and a carbonic acid diester of a lower alcohol (such as methanol).

Further examples include diene-based polyols such as polybutadiene polyols and hydrogenated products thereof; hydroxyl-containing vinyl polymers such as acrylic polyols; natural oil-based polyols such as castor oil; and modified products of natural oil-based polyols.
These polyols (A2) generally have 2 to 8, preferably 3 to 8, hydroxyl groups and usually 200 to 4,000, preferably 400 to 3,000 hydroxyl equivalents.

  The number average molecular weight of the polyol (A) [the same applies to the following number average molecular weight measured by gel permeation chromatography (GPC)] is usually 500 or more, preferably 500 to 20,000, particularly preferably 1,200 to 15: 2,000, most preferably from 2,000 to 9,000. A number average molecular weight of 500 or more is preferable in terms of foaming properties of the polyurethane foam, and a number average molecular weight of 10,000 or less is preferable in terms of low viscosity and handling properties of the polymer polyol. The hydroxyl equivalent of (A) is preferably from 200 to 4,000, and more preferably from 400 to 3,000.

In the second, third, fifth and sixth aspects of the present invention using the specific reactive dispersant (D1) or (D11), a number average usually used as described later, particularly as the ethylenically unsaturated compound (b), When only the ethylenically unsaturated compound (b2) having a molecular weight of less than 500 is used, (A1) is more preferable and (A1) is more preferable among these (A), since the obtained polyurethane has good physical properties. , (A11), or (A11) and (A12).
Polyol (A11): The average number of functional groups is 2.5 to 4, the hydroxyl value is 20 to 40 (mgKOH / g), and the content of oxyethylene units (hereinafter abbreviated as EO content) is 10 to 30% by mass. A polyoxyethylene polyoxypropylene polyol having a terminal EO content of 10 to 25% by mass (therefore, an internal EO content of 0 to 5% by mass).
Polyol (A12): a polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 2 to 6, a hydroxyl value of 15 to 130 (mgKOH / g), and an EO content of 50 to 80% by mass.

The hydroxyl value of the above (A11) is from 20 to 40 (mgKOH / g), preferably from 24 to 38. When the hydroxyl value is within this range, the viscosity of the polymer polyol composition becomes low, and the obtained polyurethane has good elongation.
(A11) can be obtained by adding EO and PO to the active hydrogen-containing compound (particularly polyhydric alcohol). The method of adding EO and PO may be block addition or random addition, but is preferably a block addition method, in which EO is added at the end and, if necessary, inside. The EO content of (A11) is from 10 to 30% by mass, preferably from 11 to 25% by mass, and more preferably from 12 to 20% by mass. The terminal EO content is 10 to 25% by mass, preferably 11 to 20% by mass. The internal EO content is 0-5% by weight. When the EO content is within the above range, the curing property at the time of polyurethane production is good.

The hydroxyl value of (A12) is 15 to 130 (mgKOH / g), preferably 18 to 120 (mgKOH / g), and more preferably 20 to 115 (mgKOH / g). When the hydroxyl value is within this range, the viscosity of the polymer polyol composition becomes low, and the resulting polyurethane has good wet heat permanent set.
(A12) can be obtained by adding EO and PO to the active hydrogen-containing compound (particularly polyhydric alcohol). The method of adding EO and PO may be block addition or random addition, but random addition is preferred, and the EO content is 50 to 80% by mass, preferably 60 to 80% by mass. And more preferably 65 to 75% by mass. If the EO content is within the above range, the polyurethane foam has good air permeability.

  The mass ratio between the polyols (A11) and (A12) in (A) is preferably from 100: 0 to 50:50, particularly preferably 99.9: 0.1 to 70:30. Within this range, a low-viscosity polymer polyol composition can be obtained.

  In the polymer polyol compositions of the first and fourth inventions, the ethylenically unsaturated compound (b) has a terminal ethylenic compound having a number average molecular weight of 160 to 490 and a solubility parameter SP of 9.5 to 13. It contains the unsaturated group-containing compound (b1) as an essential component in an amount of 5% by mass or more. The number average molecular weight of (b1) is preferably from 170 to 480, more preferably from 180 to 450, particularly preferably from 182 to 420, and most preferably from 185 to 400. When the number average molecular weight is 160 or more, the viscosity of the polymer polyol composition is low, which is preferable in terms of handleability, and the foamed foam has good hardness. When the number average molecular weight of (b1) is 490 or less, the hardness of the polyurethane foam obtained by using the same is good.

The number of ethylenically unsaturated groups in (b1) may be one or more on average. The number is preferably from 1 to 10, more preferably from 1 to 2, and particularly preferably 1. When the number of ethylenically unsaturated groups is less than one on average, not only the amount of the soluble component of the polyol increases, the viscosity of the obtained polymer polyol increases, but also the physical properties of the polyurethane resin produced by using these are remarkably inferior. . In addition, as long as the ethylenically unsaturated group of (b1) has at least one (average) terminal, the remaining unsaturated group may be present at a terminal or at a position other than the terminal even if it exists at the terminal. Is also good.
Specific examples of the above ethylenically unsaturated groups include (meth) acryloyl groups and α-alkenyl groups such as allyl groups.

Further, the molecular weight (X) per one double bond of (b1) is preferably 490 or less, more preferably 160 to 480, particularly preferably 180 to 450, and most preferably 185 to 400. When it is 490 or less, the effect of reducing the polyol-soluble oligomer in the polymer polyol produced by using them is large.
Here, the molecular weight (X) per one double bond in (b1) is defined by the following formula.
X = 1000 / N
N: the degree of unsaturation of (b1) measured by the measurement method specified in JIS K-1557

  Further, the solubility parameter SP of (b1) is usually 9.5 to 13, preferably 9.8 to 12.5, and more preferably 10.0 to 12.2. When the SP of (b1) is less than 9.5, the viscosity of the polymer polyol produced by using them becomes high. On the other hand, when the SP exceeds 13, there are disadvantages such as a decrease in hardness of the foam obtained by using the polymer polyol.

In the first and fourth inventions, the solubility parameter SP is represented by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.
[Solubility parameter] = (ΔE / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents molecular volume, and the value is represented by Robert F. Calculations by Robert F. Fedors et al., For example, are described in Polymer Engineering and Science, Vol. 14, pp. 147-154. As an example of the solubility parameter of a typical resin, as the value of the vinyl polymer, polystyrene = 10.6, polyacrylonitrile = 14.4, polymethyl methacrylate = 9.9; 9.4, polypropylene glycol = 8.7; as polyolefin, polyethylene = 8.6, polypropylene = 8.0; as polyester, polyethylene terephthalate = 12.4, polybutylene terephthalate = 11.7; polyamide The values are described as 6-nylon 11.9 and 6,6-nylon = 11.9. Other resins can also be calculated by combining the values for each chemical bond described in the table. For example, the value of polyimide is 19.6 when calculated from pyromellitic acid and 1,4-diaminobenzene, and the value of polyurethane is 12.3 when calculated from 1,4-butanediol and diphenylmethane diisocyanate. However, the values may be slightly deviated from these values due to a difference in the fine structure or the structure of the terminal of the resin.

As specific examples of (b1), the following (b11) to (b15) are preferable, since the viscosity of the polymer polyol decreases and the hardness of the obtained polyurethane foam increases, when used. You may.
(B11): (Poly) oxyalkylene (C2 to C8 alkylene group) ether of terminally unsaturated alcohol (C3 to C24) (b12): Compound represented by the following general formula [1] (b13): Compound represented by the following general formula [2] (b14): Compound represented by the following general formula [3] (b15): Compound represented by the following general formula [4] CH ₂ = CRCOO (AO) kCOCH ₂ COCH ₃ [ 1]
CH ₂ = CRCOO (AO) k [CO (CH ₂ ) sO] m (AO) nH [2]
CH ₂ = CRCO [O (CH ₂ ) sCO] mO (AO) nH [3]
CH ₂ = CRCOO (AO) k [QO (AO) p] r (QO) tH [4]
[Wherein R is a hydrogen atom or a methyl group; A is an alkylene group having 2 to 8 carbon atoms; Q is a residue obtained by removing two OH from dicarboxylic acid; k is a number average molecular weight not exceeding 490 An integer of 1 or more, n and p are 0 or an integer of 1 or more whose number average molecular weight does not exceed 490, s is an integer of 3 to 7, m and r are an integer of 1 or more whose number average molecular weight does not exceed 490, t Is 0 or 1]
Here, the number average molecular weight of "the number average molecular weight does not exceed 490" indicates the number average molecular weight of the compound.

Examples of the terminal unsaturated alcohol having 3 to 24 carbon atoms in the above (b11) include allyl alcohol and 1-hexen-3-ol. The number of oxyalkylene units of (b11) is usually 1 to 9, preferably 1 to 5, and more preferably 1 to 3.
In the above general formulas [1] to [4], A is an alkylene group having 2 to 8 carbon atoms, and the AO unit is usually formed by addition of an alkylene oxide having 2 to 8 carbon atoms, and k, n and p Each corresponds to the number of moles of the alkylene oxide added. The (poly) oxyalkylene unit having 2 to 8 carbon atoms of the alkylene group (b11) is usually formed by addition of an alkylene oxide having 2 to 8 carbon atoms.
Examples of the alkylene oxide include the same alkylene oxides as those exemplified as the alkylene oxide to be added to the active hydrogen-containing compound in the above section of the polyol (A). Preferably, it is PO and / or EO.
k is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1. n is preferably 0 or 1 to 7, more preferably 0 or 1 to 5, and particularly preferably 0. p is preferably 0 or 1 to 6.

Examples of Q include a residue obtained by removing two OH from a dicarboxylic acid. As the dicarboxylic acid, those having 4 to 10 carbon atoms are preferable, and specific examples include phthalic acid (including isophthalic acid and terephthalic acid), maleic acid, fumaric acid, and succinic acid. Preferred are phthalic acid and succinic acid.
The [CO (CH ₂ ) sO] and [O (CH ₂ ) sCO] units are usually formed by the addition of lactones. s is preferably 4 to 6, and more preferably 5. m is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2.
R is preferably 1 to 5, more preferably 1 or 2, particularly preferably 1.
Among these (b11) to (b15), more preferred are (b11) and (b12), and particularly preferred is (b11).

As specific examples of (b11) to (b15), for example, (b11) includes 1 to 5 mol of PO and / or EO of allyl alcohol.
Examples of (b12) include an acetoacetic ester of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid.
As (b13), a compound obtained by adding 1 to 5 mol of ε-caprolactone to a compound obtained by adding 1 to 5 mol of PO and / or EO to 1 mol of (meth) acrylic acid; And compounds to which お よ び 5 mol of PO and / or EO are added.
Examples of (b14) include a compound in which 1 to 5 mol of ε-caprolactone is added to 1 mol of (meth) acrylic acid, and a compound in which 1 to 5 mol of PO and / or EO is further added to 1 mol of this compound. Is mentioned.
As (b15), a monoester of a compound obtained by adding 1 to 5 mol of PO and / or EO to 1 mol of (meth) acrylic acid and an equimolar amount of succinic acid, and 1 mol of (meth) acrylic acid with PO and / or Or a monoester of maleic acid or fumaric acid in an equimolar amount with a compound obtained by adding 1 to 5 moles of EO, and an equimolar amount of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid And 1 to 5 moles of EO and / or PO further added to 1 mole of the monoester with phthalic acid, and a monoester of this compound with an equimolar phthalic acid.

  In the polymer polyol composition of the present invention, as the ethylenically unsaturated compound (b), a commonly used ethylenically unsaturated compound (b2) other than (b1) having a number average molecular weight of less than 500 may be used. As (b2), aromatic hydrocarbon monomer (b2-1), unsaturated nitriles (b2-2) (meth) acrylates (b2-3), and other ethylenically unsaturated compounds (b2-4) ), And mixtures of two or more of these. In particular, when the reactive dispersant (D1) or (D11) of the second or third invention is used, only (b2) can be used.

(B2-1) includes styrene, α-methylstyrene, hydroxystyrene, chlorostyrene and the like.
Examples of (b2-2) include acrylonitrile, methacrylonitrile, and the like.
As (b2-3), methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, Alkyl (meth) acrylates such as tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, and the like. Hydroxypolyoxyalkylene (alkylene group having 2 to 8 carbon atoms) mono (meth) acrylates;

(B2-4) includes (meth) acrylamide; vinyl group-containing carboxylic acids such as (meth) acrylic acid and derivatives thereof; aliphatic hydrocarbon monomers such as ethylene and propylene; perfluorooctylethyl methacrylate, perfluorooctyl Fluorine-containing vinyl monomers such as ethyl acrylate; nitrogen-containing vinyl monomers other than the above such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicon; and cyclic olefin compounds such as norbornene, cyclopentadiene and norbornadiene.
Among these, (b2-1) and (b2-2) are preferable, and styrene and / or acrylonitrile are more preferable. The total content of the aromatic hydrocarbon monomer and the unsaturated nitriles in (b2) is preferably 50% by mass or more.

In the second, third, fifth and sixth aspects of the present invention, (b2-1), (b2-2), (b2-3) and (b2-4) in (b) when only (b2) is used. The mass ratio 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.
(B2-1): Usually 0 to 100% by mass, preferably 20 to 80% by mass.
(B2-2): Usually 0 to 95% by mass, preferably 20 to 80% by mass.
(B2-3): Usually 0 to 50% by mass, preferably 0 to 20% by mass.
(B2-4): Usually 0 to 10% by mass, preferably 0 to 5% by mass.

  The mass ratio of (b2-1) to (b2-2) is preferably (5:95) to (100: 0), more preferably (20:80) to (100: 0), and particularly preferably. (25:75) to (80:20).

  In addition, as a part of (b) (preferably 0.05 to 1% by mass), a bifunctional or more (preferably 2 to 8 functional) polyfunctional vinyl group-containing monomer (b2 By using -5), the strength of the polymer can be further improved. Examples of polyfunctional vinyl group-containing monomers include divinylbenzene, ethylene di (meth) acrylate, polyalkylene (having 2 to 8 carbon atoms in the alkylene group) glycol di (meth) acrylate, pentaerythritol triallyl ether, and trimethylolpropane tri (meth). Acrylate and the like.

Further, as (b), an ethylenically unsaturated compound (b3) having the following number average molecular weight of 500 or more may be used.
Among (b3), those having one double bond in the molecule include unsaturated alcohols of aliphatic alcohol (C1-24) (poly) oxyalkylene (C2-8 alkylene) ether Dicarboxylic acid (C4-24) diester, for example, maleic acid diester of polyoxypropylene (degree of polymerization: n = 4-30) monomethyl ether [where the degree of polymerization n indicates the degree of polymerization of the polyoxypropylene segment I have. Hereinafter, unless otherwise specified, the degree of polymerization of the (poly) oxyalkylene segment is shown. ), Fumaric acid diester of polyoxypropylene (n = 3-30) monobutyl ether and itaconic acid diester of butanol polyoxybutylene (n = 2-20) polyoxyethylene (n = 2-10) random adduct; fat Group alcohol (C1-24) polyoxyalkylene (C2-8 alkylene group) ether (meth) acrylate, for example, polyoxypropylene [n = 8 (7) -30] monomethyl ether (meth) acrylate However, the numerical value in parentheses of n is the case of methacrylate. The same applies to the following), polyoxybutylene [n = 6 (5) to 20] monobutyl ether (meth) acrylate, and polyoxypropylene (n = 5 to 30) monolauryl ether (meth) acrylate; unsaturated alcohol (3 carbon atoms) To 24) polyoxyalkylene (alkylene group having 2 to 8 carbon atoms) ethers, for example, polyoxypropylene (n = 4 to 30) monooleyl ether, polyoxypropylene (n = 8 to 30) monoallyl ether; Saturated aliphatic monocarboxylic acid (C3-24) polyoxyalkylene (C2-8 alkylene group) ester, for example, propylene oleate (n = 2-30) -ethylene having a number average molecular weight of 500 or more Oxide (n = 2 to 10) random adduct; and the like.

  Examples of (b3) having two double bonds in the molecule include polyalkylene (C2 to C8 alkylene group) glycol di (meth) acrylate, for example, polypropylene glycol [n = 7 (6) to 30] di (meth) acrylate and polybutylene glycol [n = 6 (5) to 20] di (meth) acrylate; aliphatic carboxylic acid of unsaturated alcohol (3 to 24 carbon atoms) (2 to 24 carbon atoms) Diester, for example, succinic diester of polyoxypropylene (n = 3 to 30) monoallyl ether, adipic acid diester of polyoxypropylene (n = 3 to 30) monoallyl ether, polyoxypropylene (n = 3 to 30) Succinic diester of monopropenyl ether; and the like.

  Among (b3), those having three double bonds in the molecule include unsaturated fatty acid (3 to 24 carbon) triesters of a trihydric alcohol having 3 to 12 carbon atoms, for example, glycerin polyoxypropylene [n = 5 (4) -30] ether tri (meth) acrylate, trimethylolpropanepolyoxypropylene [n = 4 (3) -30] ether tri (meth) acrylate, pentaerythritol polyoxypropylene [n = 4 ( 3) to 30] ether tri (meth) acrylate, diglycerin polyoxypropylene (n = 3 to 30) ether tri (meth) acrylate, and sorbitan polyoxybutylene [n = 3 (2) to 20] tri ( (Meth) acrylate; aliphatic carboxylic acid (3 to 24 carbon atoms) of unsaturated alcohol (3 to 24 carbon atoms) Ster, for example, hexanetricarboxylic acid triester of allyl alcohol (poly) oxypropylene (n = 1 to 30) ether; unsaturated alkyl group-containing ether compound, for example, glycerin polyoxypropylene (n = 5 to 30) ether triester Allyl ether; and the like.

  Examples of (b3) having four or more double bonds in the molecule include unsaturated fatty acid (3 to 24 carbon atoms) polyesters of polyvalent (4 to 8 or more) alcohols, for example, Polyglycerin having an average molecular weight of 500 or more (degree of polymerization of glycerin: n = 3 to 4) poly (meth) acrylate (hereinafter, for a polyglycerin group, n indicates the degree of polymerization of glycerin), and a number average molecular weight of 500 or more (N = 2-4) polyolate, dipentaerythritol poly (meth) acrylate having a number average molecular weight of 500 or more, polyglycerin (n = 2-4) (poly) oxypropylene having a number average molecular weight of 500 or more (N = 1-30) Poly (meth) acrylate, pentaerythritol polyoxypropylene [n = 3 (2) -30] ether tetra (Meth) acrylate, tetra (meth) acrylate of sorbitan polyoxybutylene (n = 2 to 20) ether, polyvinyl alcohol (degree of saponification 70 to 100, number average molecular weight 1,000 to 10,000) (meth) acrylate; Polycarboxylic acid esters (number average molecular weight: 1,000 to 10,000) of saturated alcohols (3 to 24 carbon atoms), for example, hexane tetracarboxylic acid esters of allyl alcohol (poly) oxypropylene (n = 1 to 30) ether Polyester of (meth) acrylic acid polymer and allyl alcohol (number average molecular weight 1,000 to 10,000), polyester of maleic acid polymer and allyl alcohol (number average molecular weight 1,000 to 10,000); unsaturated alkyl group Containing ether compound, for example, number average molecular weight 5 0 or more tetraglycerin polyallyl ether, polyallyl ether of polyglycerin (n = 2-4) (poly) oxypropylene (n = 1-30) ether having a number average molecular weight of 500 or more; unsaturated carboxylic acid (4 carbon atoms) To 22) and glycols (number average molecular weight of 500 to 10,000), for example, polyester of maleic acid and ethylene glycol (number average molecular weight of 500 to 10,000), polyester of maleic acid and diethylene glycol (number average) Polyester of maleic acid and propylene glycol (number average molecular weight of 500 to 10,000), polyester of maleic acid and 1,3- or 1,4-butanediol (number average molecular weight of 500 to 10,000) 000), poly of itaconic acid and ethylene glycol Ester (number average molecular weight 500 to 10,000), polyester of itaconic acid and diethylene glycol (number average molecular weight 500 to 10,000), polyester of maleic acid and polyoxypropylene glycol (n = 1 to 30) (number average molecular weight) 500-10,000), polyester (number average molecular weight 500-10,000) of itaconic acid and polyoxypropylene glycol (n = 1-30), and fumaric acid and polyoxybutylene glycol (n = 1-20). (Number average molecular weight of 500 to 10,000); and the like.

Of these (b3), an ester compound comprising an unsaturated carboxylic acid (p) and a glycol (q) and / or an ester compound comprising an unsaturated alcohol (r) and a carboxylic acid (s) are preferable. A radical polymerizable compound comprising a saturated carboxylic acid (p) and a glycol (q) is particularly preferred.
The unsaturated carboxylic acid (p) is a carboxylic acid having a double bond (a non-conjugated double bond in the case of two or more) or a derivative thereof in the molecule, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. C3 to C24 carboxylic acids such as acid, itaconic acid, citraconic acid and oleic acid; and acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. Preferably, it is at least one carboxylic acid selected from maleic acid, fumaric acid and itaconic acid, or a derivative thereof.
If necessary, other carboxylic acids can be used in combination. Other carboxylic acids include, for example, aliphatic carboxylic acids having 2 to 24 carbon atoms such as acetic acid, propionic acid, hexanoic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid and sebacic acid; C7 to C18 aromatic carboxylic acids such as acids and terephthalic acids; C6 to C20 alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid and tetrahydrophthalic acid.

  As the glycols (q), among the active hydrogen-containing compounds described in the description of the polyol (A), polyhydric alcohols and polyphenols, and the alkylene oxides having 2 to 8 carbon atoms can be used. Preferably, alkylene glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polyoxypropylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and EO, PO , BO, SO and the like, and more preferably, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, EO and PO.

The content of (b1) in (b) is preferably 2% by mass or more, more preferably 5 to 80% by mass, and particularly preferably 7 to 50% by mass.
When the amount of (b1) is 2% by mass or more, the viscosity of the obtained polymer polyol becomes low. (B1) is preferably 5% by mass or more [the first and fourth inventions], but when the reactive dispersant (D1) (including (D11)) described below is used, even if it is less than 5% by mass. No problem. The component in (b) used in combination with (b1) is preferably (b2).

  Examples of the polymerization method (b) include radical polymerization, coordination anion polymerization, metathesis polymerization, Diels-Alder polymerization, and the like. Radical polymerization is preferred.

The radical polymerization can be performed in the same manner as the polymerization in the conventional polymer polyol. For example, a method of polymerizing an ethylenically unsaturated compound (b) in the presence of a polymerization initiator in a polyol (A) containing a dispersant (D) (a method described in US Pat. No. 3,383,351) is known. No.
The polymerization can be carried out in a batch system or a continuous system, and can be carried out under normal pressure, under pressure or under reduced pressure. If necessary, a diluent (C), a chain transfer agent and the like can be used.
Hereinafter, each component used for radical polymerization will be described sequentially.

The dispersant (D) is not particularly limited, and the following general dispersants used in polymer polyols can be used.
For example, [1] a macromer-type dispersant obtained by reacting a polyol such as an ethylenically unsaturated group-containing modified polyether polyol (for example, JP-A-08-333508) with an ethylenically unsaturated compound; Two or more polyol affinity segments having a solubility parameter difference of 1.0 or less as side chains, and a polymer affinity segment having a solubility parameter difference of 2.0 or less from a polymer derived from a vinyl monomer as a main chain. A graft-type dispersant in which a polyol and an oligomer such as a graft-type polymer (for example, Japanese Patent Application Laid-Open No. 05-059134) are combined; [3] at least a part of the hydroxyl groups of the polyol is methylene dihalide and / or ethylene dihalide; Modified polyol having a high molecular weight by reacting with a halide (for example, Japanese Patent Application Laid-Open No. 07-196749) And (4) a vinyl-based oligomer having a weight-average molecular weight of 1,000 to 30,000, at least a part of which is soluble in a polyol, and the oligomer and the ethylenically unsaturated monomer of the above (1). Oligomer-type dispersants such as dispersants that use a group-containing modified polyether polyol in combination (for example, JP-A-09-77968); and the like.
Of these, the types [1] and [4] are preferred. In each case, the number average molecular weight is preferably 1,000 to 10,000.
In addition, when these ordinary dispersants are used as (D), the amount used is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 0.1 to 10% by mass, based on the mass of (b). 8% by mass.

As (D), in addition to these ordinary dispersants, the following reactive dispersants (D1) (including (D11)) of the present second, third, fifth and sixth inventions are used. Is particularly preferred.
The reactive dispersant (D1) is obtained by bonding a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group to a substantially saturated polyol (a) via a polyisocyanate (f). This is a dispersant comprising the obtained nitrogen-containing bond-containing unsaturated polyol.

As (a) constituting the reactive dispersant (D1), the same ones as those exemplified as the above (A) can be used. (A) and (A) may be the same or different.
The number of hydroxyl groups in one molecule of (a) is at least 2, preferably 2 to 8, more preferably 3 to 4, and the hydroxyl equivalent of (a) is preferably 1,000 to 3, 000, more preferably 1,500 to 2,500.

(E) used to obtain (D1) is a compound having one active hydrogen-containing group and at least one polymerizable unsaturated group. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, an imino group, a carboxyl group, and an SH group, and a hydroxyl group is particularly preferable.
The polymerizable unsaturated group of (e) is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably from 1 to 3, particularly preferably 1. That is, an unsaturated monohydroxy compound having one polymerizable double bond is preferable as (e).
Examples of the unsaturated monohydroxy compound include a monohydroxy-substituted unsaturated hydrocarbon, a monoester of an unsaturated monocarboxylic acid and a dihydric alcohol, a monoester of an unsaturated dihydric alcohol and a monocarboxylic acid, and an alkenyl side chain. Examples include phenol having a group and unsaturated polyether monool.

Examples of the monohydroxy-substituted unsaturated hydrocarbon include alkenols having 3 to 6 carbon atoms, such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, and 3-buten-1-ol; Alkynol, for example, propargyl alcohol and the like.
Examples of the monoester of an unsaturated monocarboxylic acid and a dihydric alcohol include, for example, an unsaturated monocarboxylic acid having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; And monohydric esters having 2 to 12 carbon atoms such as glycol, propylene glycol, and butylene glycol, and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and the like.

Examples of the monoester of an unsaturated dihydric alcohol and a monocarboxylic acid include monoesters of an unsaturated dihydric alcohol having 3 to 8 carbon atoms and a monocarboxylic acid having 2 to 12 carbon atoms such as acetic acid monoester of butenediol. Is mentioned.
Examples of the phenol having an alkenyl side chain group include phenols having an alkenyl side chain group having 2 to 8 carbon atoms in an alkenyl group such as oxystyrene and hydroxy α-methylstyrene.
As the unsaturated polyether monool, 1 to 50 mol adduct of the above-mentioned monohydroxy-substituted unsaturated hydrocarbon or the above-mentioned alkylene oxide (2 to 8 carbon atoms) of phenol having an alkenyl side chain group [for example, polyoxyethylene (polymerization degree 2 to 10) monoallyl ether].

Examples of (e) other than the unsaturated monohydroxy compound include the following.
Examples of (e) having an amino group or an imino group include mono- and di- (meth) allylamine, aminoalkyl (2-4 carbon atoms) (meth) acrylate (such as aminoethyl (meth) acrylate), monoalkyl (carbon (Equation 1 to 12) aminoalkyl (C2 to C4) (meth) acrylate [such as monomethylaminoethyl-methacrylate]; (e) having a carboxyl group includes the unsaturated monocarboxylic acid described above; )) Includes compounds corresponding to the unsaturated monohydroxy compounds (OH is replaced by SH).
Examples of (e) having two or more polymerizable double bonds include poly (meth) allyl ether of the above-mentioned trivalent, 4- to 8-valent or more polyhydric alcohol or polyester with the above unsaturated carboxylic acid. [For example, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, etc.].

Among these compounds, preferred are alkenol having 3 to 6 carbon atoms, monoester of an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and a dihydric alcohol having 2 to 12 carbon atoms, and phenol having an alkenyl side chain group. And more preferably monoesters of (meth) acrylic acid with ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, and particularly preferably 2-hydroxyethyl (meth) acrylate.
The molecular weight of (e) is not particularly limited, but is preferably 1,000 or less, particularly preferably 500 or less.

  The polyisocyanate (f) is a compound having at least two isocyanate groups, and is an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, or a modified product of these polyisocyanates (urethane Group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group or oxazolidone group-containing modified product), isocyanate group-terminated prepolymer, and a mixture of two or more of these.

Examples of the aromatic polyisocyanate include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same applies to the following polyisocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates And the like. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4 ' Diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminodiphenylmethane @ formaldehyde and an aromatic amine (aniline) or a mixture thereof: Phosgenated product of poly (II): polyallylpolyisocyanate (PAPI), etc.]
, Naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.
Examples of the aliphatic polyisocyanate include an aliphatic diisocyanate having 2 to 18 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include an alicyclic diisocyanate having 4 to 16 carbon atoms. Specific examples include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic isocyanates include araliphatic diisocyanates having 8 to 15 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
Of these, aromatic diisocyanates are preferred, and 2,4- and / or 2,6-TDI are more preferred.

The nitrogen-containing bond of the reactive dispersant (D1) is generated by a reaction between an isocyanate group and an active hydrogen-containing group. When the active hydrogen-containing group is a hydroxyl group, a urethane bond is mainly formed and an amino group is formed. In some cases, mainly urea bonds are formed. An amide bond is formed in the case of a carboxyl group, and a thiourethane bond is formed in the case of an SH group. In addition to these groups, other bonds such as a burette bond and an allophanate bond may be formed.
This nitrogen-containing bond is formed by a reaction between a hydroxyl group of a substantially saturated polyol (a) and an isocyanate group of a polyisocyanate (f), and an active hydrogen-containing group of an unsaturated monofunctional active hydrogen compound (e). and f) by reaction with isocyanate groups.

In light of the dispersion stability of the polymer polyol, the average value of the number of hydroxyl groups in one molecule of (D1) is usually 2 or more, preferably 2.5 to 10, and more preferably 3 to 6. The average value of the number of unsaturated groups in one molecule of (D1) is preferably 0.8 to 2, and more preferably 0.9 to 1.2.
From the viewpoint of dispersion stability of the polymer polyol, the hydroxyl equivalent of (D1) is preferably from 500 to 10,000, more preferably from 1,000 to 7000, particularly preferably from 2,000 to 6,000.
The viscosity of (D1) is preferably 10,000 to 50,000 mPa · s / 25 ° C., and more preferably 15,000 to 35,000 mPa · s / 25 ° C. When the viscosity is within the above range, the dispersibility of the polymer is better, and the viscosity of the polymer polyol obtained by using (D1) is low, and handling is easy.

The method for producing the reactive dispersant (D1) using these raw materials is not particularly limited.
As a preferable method, a method of adding a polyisocyanate (f) to a mixture of an unsaturated monofunctional active hydrogen compound (e) and a substantially saturated polyol (a), and reacting the mixture in the presence of a catalyst if necessary, (E) and (f) are optionally reacted in the presence of a catalyst to produce an unsaturated compound having an isocyanate group, and then reacted with (a). The latter method is the most preferable method because it is a method that can obtain a nitrogen-containing bond-containing unsaturated polyol with less generation of by-products such as a compound having no hydroxyl group.
Alternatively, after reacting with (f) using the precursor instead of (e) or (a), the precursor portion may be modified to form (D1). [For example, an unsaturated monocarboxylic acid or an ester-forming derivative thereof is reacted after reaction with an isocyanate to introduce an unsaturated group. Form〕

Examples of the catalyst at the time of the above reaction include, for example, a commonly used urethane-forming catalyst, such as a tin-based catalyst (such as dibutyltin dilaurate and Starnas octoate), another metal catalyst (such as tetrabutyl titanate), and an amine-based catalyst ( Triethylenediamine and the like are used. Preferred among these is tetrabutyl titanate.
The amount of the catalyst is preferably 0.0001 to 5% by mass, more preferably 0.001 to 3% by mass, based on the mass of the reaction mixture.

As for the reaction ratio of these three components, the equivalent ratio of the active hydrogen-containing group of (e) and (a) to the isocyanate group of (f) is preferably (1.2 to 4) based on the total amount used in the reaction. : 1, more preferably (1.5 to 3): 1.
The amount of (e) used in the reaction with respect to 100 parts by mass of (a) is preferably less than 2 parts by mass, more preferably 0.5 to 1.8 parts by mass.

  The reactive dispersant (D1) obtained by the above method may be a single compound, but in many cases, a mixture of various compounds represented by the following general formula [5].

Wherein, Z is acid residue (except h is an integer of 2 or more) of the h value (f); T is (with the proviso, polymerizable unsaturated group.) Residue (e); A ₁ is q residues of _monovalent polyol [(a), or OH prepolymer from (a) and (f)], a ₂ is q ₂ dihydric polyol [(a), or (a) and from (f) OH prepolymer] (where q ₁ and q ₂ are integers of 2 or more); X is a single bond, O, S, or —N—;
|
T '
T 'is H or an alkyl group having 1 to 12 carbon atoms; g is an integer of 1 or more; j is an integer of 1 or more. However, q ₁ −g ≧ 0 and h−j−1 ≧ 0. The total number of OH groups is 2 or more. ]

That is, one (a) and one (e) are connected through one (f), and a plurality of (e) are each connected to one (a) through one (f). ), And a combination of a total of three or more (a) and (e) via a plurality of (f). In addition, as other by-products, (a) one having a bond bonded via (f) (a nitrogen-containing bond-containing polyol having no unsaturated group), and (e) having a bond bonded via (f) (A unsaturated compound containing a nitrogen-containing bond having no hydroxyl group) may be formed, and may contain unreacted (a) or (e).
This mixture can be used as a dispersant as it is, but those containing a small amount of a nitrogen-containing bond-containing polyol having no unsaturated group or a nitrogen-containing bond-containing unsaturated compound having no hydroxyl group are preferable, and these impurities which can be further removed are preferable. Can also be applied after removal.
Further, since the unsaturated group in (D1) is located at or near the terminal of the molecular chain of the polyol, it is easy to copolymerize with the monomer.

(D11) used in the third and sixth inventions is an average of the ratio of the number of unsaturated groups to the nitrogen-containing bond derived from the NCO group of (f) in one molecule, which is determined by the following formula (4): K (A), (e) and (f) are reacted at such a ratio that is 0.1 to 0.4.
K = [number of moles of (e) × number of unsaturated groups of (e)] / [number of moles of (f) × number of NCO groups of (f)]
−−−− (4)
The value of K is more preferably from 0.1 to 0.3, and particularly preferably from 0.2 to 0.3. When the value of K is within the above range, the dispersion stability of the polymer polyol becomes particularly good.

The constituent ratio of the polyol (A) and the reactive dispersant (D1) at the time of preparing the polymer polyol is preferably such that 0.5 to 50 parts by mass of (D1) is used with respect to 100 parts by mass of (A). Second and fifth inventions]. More preferably, (D1) is 0.8 to 15 parts, particularly preferably 1 to 10 parts, per 100 parts of (A). When (D1) is 50 parts by mass or less, the viscosity of the polymer polyol does not increase, and when it is 0.5 parts by mass or more, the dispersibility is good.
In the case of (D11), since the dispersion stability is excellent, the use ratio can be changed in a wide range (for example, 0.1 to 80 parts by mass with respect to 100 parts by mass of (A)), but the above range is preferable.

  The reactive dispersants (D1) and (D11) of the second, third, fifth, and sixth inventions have very good dispersion stability of the polymer polyol composition obtained by using them, and As the unsaturated compound, it can be used for producing a polymer polyol composition using only the conventional monomer (b2), but the specific ethylenically unsaturated group-containing compound (b1) of the first and fourth inventions is used. It is particularly suitably used for the production of a polymer polyol composition, and a polymer polyol composition having a lower viscosity can be obtained.

  Next, as the radical polymerization initiator used in the polymerization of (b), those which generate free radicals and initiate polymerization can be used. For example, 2,2′-azobisisobutyronitrile, 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2 , 4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and 1,1'-azobis ( Azo compounds such as 1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate DOO, benzoyl peroxide, organic peroxides such as lauroyl peroxide and peracetic acid; inorganic peroxides such as persulfates and perborate salts. In addition, these can use 2 or more types together.

  The amount used when the radical polymerization initiator is used is usually 0.05 to 20% by mass, preferably 0.1 to 15% by mass, and particularly preferably 0.2 to 10% by mass, based on the amount of (b) used. %. When the amount of the polymerization initiator used is in the range of 0.05 to 20% by mass, the polymerization rate of (b) in the polymer polyol becomes sufficiently high and the molecular weight also becomes large, so that when the urethane foam is used, a sufficient foam is obtained. It is excellent in that compression hardness can be obtained.

Examples of polymerization initiators in polymerization methods other than radical polymerization include, in coordination anion polymerization, organic alkyl compounds of metals of Groups I, II and III of the periodic table and metal salts of Groups IV to VII. An initiator consisting of a combination is mentioned. In the metathesis polymerization, an initiator composed of a combination of WCl ₆ or MoCl ₅ and organoaluminum is used.

Examples of the diluent (C) used in the radical polymerization include aromatic hydrocarbon solvents such as toluene and xylene; saturated aliphatic hydrocarbon solvents having 5 to 15 carbon atoms such as hexane and heptane; octene, nonene and decene. C5-30 unsaturated aliphatic hydrocarbon solvents; alcohol solvents such as methanol, isopropanol and n-butanol; ether solvents such as dioxane; ester solvents such as ethyl acetate; nitriles such as acetonitrile Amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. Preferred as (C) is an aromatic hydrocarbon-based solvent, more preferably xylene, because the viscosity of the obtained polymer polyol composition becomes low.
The amount of the diluent to be used is preferably 0 to 50% by mass, more preferably 1 to 40% by mass, based on the amount of (b) used.

The (C) used is preferably removed by vacuum stripping or the like after the polymerization reaction. However, if necessary, the (C) may be left in the polymer polyol composition (I) or may be newly added to the polymer polyol composition (I). ) Can be further reduced in viscosity. Examples of (C) contained in (I) include the above-mentioned unsaturated aliphatic hydrocarbon solvents; aromatic solvents; and low-viscosity (100 mPa · s / 25 ° C. or less) flame retardants, for example, tris (chloroethyl). Phosphate, tris (chloropropyl) phosphate; and the like.
The content of (C) in (I) is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

Examples of the chain transfer agent include alkyl mercaptans such as dodecyl mercaptan and mercaptoethanol; alcohols such as isopropyl alcohol, methanol, 2-butanol and allyl alcohol; and halogenated carbons such as carbon tetrachloride, carbon tetrabromide and chloroform. Hydrogen and the like.
The amount of the chain transfer agent to be used is usually 0 to 2% by mass based on the amount of (b) used.

  The content of the polymer particles (B) dispersed in (A) in the polymer polyol composition of the first to third inventions is preferably 35 to 75 mass, particularly when (b) is composed of (b1). %, More preferably 45 to 75% by mass. When the content of (B) is 35% by mass or more, sufficient foam compression hardness is obtained, and when it is 75% by mass or less, aggregation and sedimentation of polymer particles can be prevented, and a polymer polyol having good handleability can be obtained. Is preferred.

In the polymer polyol composition (I) of the first to third inventions obtained by the production method of the fourth to sixth inventions, the content of (B) is 35 to 75% by mass based on the mass of (I). In particular, when (b) comprises (b1), the amount of the soluble polymer (P) dissolved in (A) can be 5% by mass or less based on the mass of (A). The amount of (P) is preferably at most 3% by mass. When the amount of (P) is 5% by mass or less, the viscosity of the polymer polyol composition is low, the handling is easy, and the hardness of the foamed foam increases. In the case of the polymer polyol composition (I) obtained using the dispersant (D), the content of (P) is preferably 5% by mass or less, but may be 10% by mass or less.
Here, the soluble polymer (P) dissolved in the polyol (A) refers to the polymer particles (B) insoluble in (A) and the polymer particles (A) (a small amount of low molecular weight additive) from the polymer polyol composition (I). (Including living organisms) and is usually a compound having a higher molecular weight than the polyol (A).

The content of the polymer particles (B) and the amount of the soluble polymer (P) are measured by the following methods.
20 g of methanol is added to 5 g of (I), and the mixture is placed in a 100 cc stainless steel tube and centrifuged at 20 ° C. at 18,000 rpm × 60 minutes to aggregate (B), thereby obtaining a clear supernatant solution. The ratio (%) of the obtained mass of (B) to (I) is defined as the content of (B). After methanol was removed from this solution by a reduced-pressure drier, a polyol (A) (including a small amount of low-molecular-weight by-product) and a polymer (P) soluble in (A) (weight average) were obtained by preparative liquid chromatography. (A molecular weight of 4000 or more, a peak generally appears on the higher molecular weight side than the peak of (A) in chromatography). The weight average molecular weight (by GPC) of (P) is usually from 6,000 to 30,000, but may further include those having a higher molecular weight.
When the soluble polymer (P) cannot be separated from the polyol (A) by preparative liquid chromatography (when the molecular weights are overlapped), centrifugation is carried out in the same manner as described above to aggregate (B), and the supernatant clear solution is used. Get. After methanol is removed from this solution by a reduced-pressure drier, diethyl ether is added, and the precipitate is separated by filtration and dried, whereby the soluble polymer (P) can be separated from (A).

The polymer polyol compositions (I) of the first to third inventions obtained by the production methods of the fourth to sixth inventions have a content of (B) of 35 to 75 based on the mass of (I). %, Especially when (b) consists of (b1), the viscosity V (mPa · s) of the (I) measured at 25 ° C. by a Brookfield viscometer is within the range of the following formula (1), preferably A polymer polyol composition having a range satisfying both of the following formulas (2) and (3) can be obtained.
V ≦ (Va−Va × C / 10) ＾ [e ＾ x] (1)
V ≦ (Va−Va × C / 10) ＾ [e ＾ y] (2)
V ≧ 0.5 × (Va−Va × C / 10) ＾ [e ＾ y] (3)
However, x = 0.0010354 × Bp ＾ 1.5
y = 0.0009514 × Bp ＾ 1.5
Va: Viscosity (mPa · s) of (A) at 25 ° C. measured by a Brookfield viscometer.
C: Content of (C) in (I) (% by mass)
Bp: Content of (B) in (I) (% by mass)
＾: Indicates a power.
e: base of natural logarithm.

However, V and Va are measured under the following conditions.
1500mPa · s or less; rotor NO.3, 60rpm
1500-3000mPa · s; rotor NO.3, 30rpm
3000-8000mPa · s; rotor NO.3, 12rpm
8000 ~ 16000mPa ・ s; rotor No.3, 6rpm
16000-40000mPa · s; rotor NO.4, 12rpm
4000 ~ 100,000mPa ・ s; Rotor NO.4, 6rpm
Within the range of the above formula (1), the polymer polyol composition (I) has a better mixability with other raw materials, and the polymer polyol composition has good handleability.

The method for producing a polyurethane resin of the seventh invention is a method for producing a polyurethane resin comprising using the polymer polyol composition (I) according to any one of the first to third inventions as at least a part of a polyol component. is there.
In a method for producing a polyurethane resin by reacting a polyol component and a polyisocyanate component, if necessary, in the presence of a foaming agent, a catalyst, a foam stabilizer, and other additives, a polyol component other than the polymer polyol composition of the present invention. If necessary, it can be used in combination with other known active hydrogen atom-containing compounds. As other active hydrogen atom-containing compounds, other high molecular polyols or monools (T) and low molecular weight active hydrogen atom-containing compounds (U) commonly used in the production of polyurethane can be used.

As other polymer polyols or monools (T), polyether polyols, polyester polyols, other various polyols or monols, and mixtures thereof can be used.
Examples of the polyether polyol include those similar to the polyether polyol exemplified in the section of the polyol (A1).
Examples of the polyester polyol include those exemplified as the polyester polyol (A2).
Other polyols or monols other than these include diene-based polyols such as polybutadiene polyols and hydrogenated products thereof; hydroxyl-containing vinyl polymers such as acrylic polyols; natural oil-based polyols such as castor oil; modification of natural oil-based polyols Products: Active hydrogen compounds having terminal-radical polymerizable functional groups described in WO 98/44016 (including monools); polymer polyols other than the present invention can also be used.

These other polymer polyols or monools (T) preferably have 2 to 8, more preferably 3 to 8 hydroxyl groups and usually 200 or more, preferably 300 to 4000, more preferably 400 to 3000 Has a hydroxyl equivalent.
Particularly preferred are polyether polyols.

The low molecular weight active hydrogen atom-containing compound (U) has at least 2 (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl group, amino group, mercapto group and the like, preferably hydroxyl group). Compounds having an equivalent per active hydrogen atom of less than 200 (preferably 30 to 180) are exemplified. The molecular weight of (U) is preferably 500 or less, more preferably 60 to 400.
Examples of (U) include low molecular polyols and amino alcohols.

Examples of the low molecular polyol include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α Polyhydric alcohols having 3 to 8 or more valences such as methyl glucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose; low molecular weight (for example, 200 to 400) polyhydric alcohol alkylene oxide addition (Polyethylene glycol, polypropylene glycol, etc.); low molecular weight diols having a ring structure, for example, a propylene oxide adduct of bisphenol A and the like. It is.
Amino alcohols include mono- or dialkanolamines (such as monoethanolamine, diethanolamine, monopropanolamine).
Preferred among these are low molecular weight polyols, especially diols, specifically ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and mixtures of two or more of these. is there.

The amount of the polymer polyol composition (I) of the present invention in the polyol component (Z) [(I) and, if necessary, (T) and / or (U)] used for the production of the polyurethane resin is preferably 5% by mass or more. , More preferably at least 10% by mass, particularly preferably at least 20% by mass. When the content is 5% by mass or more, the compression hardness of the foam in the case of urethane foam is easily obtained.
The content of (B) in (Z) is preferably 5 to 75% by mass, more preferably 7 to 55% by mass. Within the above range, both foam hardness and liquid flowability are good.

Further, the content of (T) is preferably 0 to 95% by mass, more preferably 0 to 80% by mass. When the (T) is 95% by mass or less, the foam has a high compression hardness.
The content of (U) is preferably 0 to 30% by mass, and more preferably 0 to 10% by mass. When (U) is 30% by mass or less, the exothermic temperature during the reaction does not become too high, and there is no possibility that scorch is generated.

As the polyisocyanate component used for producing the polyurethane resin of the seventh invention, a known organic polyisocyanate conventionally used for producing a polyurethane resin can be used.
Examples of such a polyisocyanate include those described above as the polyisocyanate (f).
Preferred among these are 2,4- and 2,6-TDI, mixtures of these isomers, crude TDI; 4,4'- and 2,4'-MDI, mixtures of these isomers, crude MDI; and modified polyisocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, and isocyanurate groups derived from these polyisocyanates.

  The isocyanate index [equivalent ratio of (NCO group / active hydrogen atom-containing group) × 100] in the production of the polyurethane resin is usually 80 to 140, preferably 85 to 120, and particularly preferably 95 to 115. The polyisocyanurate group can also be introduced into the polyurethane by setting the isocyanate index significantly higher than the above range (for example, 300 to 1000).

In the production of the polyurethane resin, a catalyst generally used for a polyurethane reaction may be used to accelerate the reaction. For example, amine catalysts [tertiary amines such as triethylenediamine, N-ethylmorpholine, bis-2-dimethylaminoethyl ether; 1,8-diaza-bicyclo [5.4.0] undecene-7 (DBU, manufactured by San Apro Co.) ); Etc.), tin-based catalysts (stannous octoate, dibutyltin dilaurate, etc.), other metal catalysts (lead octoate, etc.) and isocyanuration catalysts described in U.S. Pat. No. 4,299,924. No. Among them, amine catalysts and / or tin catalysts are preferred.
When the catalyst is used, the amount used is preferably 0.001 to 5% by mass, based on the mass of the reaction mixture.

In the production method of the present invention, a polyurethane foam (preferably having an expansion ratio of 5 to 100 times) can be used, if necessary, by using a blowing agent usually used for a polyurethane reaction.
As the blowing agent, at least one selected from hydrogen atom-containing halogenated hydrocarbons, water, low-boiling hydrocarbons, liquefied carbon dioxide, and the like is used.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon,
HCFC (hydrochlorofluorocarbon) type (eg, HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b)
HFC (hydrofluorocarbon) type (eg, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc)
And the like.
Among these, preferred are HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, and a combination of two or more thereof.
The low-boiling hydrocarbon is a hydrocarbon having a boiling point of usually -5 to 70C, and specific examples thereof include butane, pentane, cyclopentane, and a mixture thereof.

When the halogenated hydrocarbon compound containing a hydrogen atom is used, the amount is usually not more than 50 parts by mass, preferably 5 to 45 parts by mass, per 100 parts by mass of the polyol component (Z).
When the low boiling point hydrocarbon is used, the amount used is usually not more than 45 parts by mass, preferably 5 to 40 parts by mass, per 100 parts by mass of (Z).
When liquefied carbon dioxide gas is used, the amount used is usually not more than 30 parts by mass, preferably 5 to 25 parts by mass, per 100 parts by mass of (Z).
When a hydrogen atom-containing halogenated hydrocarbon is used in combination with water, the amount of the hydrogen atom-containing halogenated hydrocarbon is usually not more than 45 parts by mass, preferably 5 to 40 parts by mass per 100 parts by mass of (Z). And the amount of water to be used is usually not more than 10 parts by mass, preferably 0.5 to 8 parts by mass, per 100 parts by mass of (Z).
When low-boiling hydrocarbons and water are used in combination, the amount of low-boiling hydrocarbons used is usually not more than 40 parts by mass, preferably 2 to 35 parts by mass, per 100 parts by mass of (Z). The amount used is usually not more than 10 parts by mass, preferably 0.5 to 8 parts by mass, per 100 parts by mass of (Z).
When liquefied carbon dioxide and water are used in combination, the amount of liquefied carbon dioxide used is usually not more than 25 parts by mass, preferably 0.1 to 20 parts by mass, per 100 parts by mass of (Z). The amount used is usually not more than 10 parts by mass, preferably 0.5 to 8 parts by mass, per 100 parts by mass of (Z).
When only water is used alone as the blowing agent, the amount of water to be used is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of (Z).

In the method for producing a polyurethane resin or a foam thereof of the present invention, if necessary, the reaction may be carried out in the presence of a foam stabilizer or other additives as described below.
As the foam stabilizer, any one used in the production of ordinary polyurethane foams can be used. Examples thereof include dimethylsiloxane-based foam stabilizers [for example, “SRX-253” manufactured by Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd. "F-122" manufactured by Kogyo Co., Ltd.], a polyether-modified dimethylsiloxane-based foam stabilizer [for example, "L-5309", "L-3601", "SZ-1311" manufactured by Nippon Unicar Co., Ltd.] And the like, and "F-242T" manufactured by Shin-Etsu Chemical Co., Ltd. and the like].
In addition, coloring agents (dyes, pigments, carbon black, etc.), plasticizers (phthalates, adipates, etc.), organic fillers (synthetic short fibers, hollow microspheres made of thermoplastic or thermosetting resin, etc.), Inorganic fillers (inorganic salts (calcium carbonate, barium sulfate, etc.), inorganic fibers (glass fibers, carbon fibers, etc.), whiskers (potassium titanate whiskers, etc.), flame retardants (phosphate esters, halogenated phosphate esters) , Melamines, phosphazene derivatives, etc.), anti-aging agents (triazoles, benzophenones, etc.), antioxidants (hindered phenols, hindered amines, etc.), adhesives (modified polycaprolactone polyol, etc.), internal mold release The reaction can be carried out in the presence of a known additive such as an agent or a bactericide.

  With respect to the amount of these additives to be used with respect to 100 parts by mass of the polyol component (Z), the foam stabilizer is preferably 10 parts by mass or less, more preferably 0.2 to 5 parts by mass. The colorant is preferably at most 1 part by mass. The amount of the plasticizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The amount of the organic filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. The amount of the inorganic filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. The amount of the flame retardant is preferably 20 parts by mass or less, more preferably 5 to 15 parts by mass. The antioxidant is preferably 1 part by mass or less, more preferably 0.01 to 0.5 part by mass. The amount of the antioxidant is preferably 1 part by mass or less, more preferably 0.01 to 0.5 part by mass. The above-mentioned additives other than these are preferably 1 part by mass or less.

The polyurethane resin can be produced by a usual method, and can be produced by a known method such as a one-shot method, a semi-prepolymer method, a prepolymer method, or the like.
For the production of the polyurethane resin, a commonly used production apparatus can be used. In the case of no solvent, for example, a device such as a kneader or an extruder can be used. For example, various non-foamed or foamed polyurethane resins can be manufactured in a closed mold or an open mold. The pack ratio [(density at the time of mold foaming / density at the time of free foaming) × 100] in the case of producing a foamed polyurethane resin using a closed mold is preferably 110 to 200%.
The production of a polyurethane resin is usually carried out by mixing and reacting raw materials using a low-pressure or high-pressure mechanical device. Further, before and after the mixing of the raw materials (particularly before the mixing of the raw materials), the polyurethane resin can be produced by removing gases such as dissolved air in the raw materials or air mixed during mixing by a vacuum method.

The polymer polyol obtained by the production method of the present invention is useful for producing a polyurethane foam, particularly a flexible mold foam and a slab foam. It can also be applied to molding by the RIM (reaction injection molding) method.
The polyurethane resin produced by using the polymer polyol composition of the present invention is used, for example, as a polyurethane foam for interior preparation of automobile interior parts, furniture and the like. It is also used as a material for sealants and synthetic leather.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the following, parts,%, and ratio indicate parts by mass, mass%, and mass ratio, respectively.

The compositions, symbols, and the like of the raw materials used in the following production examples are as follows.
(1) Unsaturated monofunctional active hydrogen compound (e)
HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate (2) Catalyst for production of reactive dispersant TBT: tetrabutyl titanate [manufactured by Nacalai Tesque, Ltd.]
(3) Polyisocyanate for production of reactive dispersant (f)
TDI: Coronate T-80 [manufactured by Nippon Polyurethane Co., Ltd.]
(4) Polyol (a)
Polyol (a-1): a polyol having an EO content of 12% and a hydroxyl value of 32 obtained by adding 104 mol of PO on average to pentaerythritol and then adding 19 mol of EO on average.

<Production Example 1> Production of reactive dispersant (D1) -1
In a 500 mL four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel, 28 parts (0.16 mol) of TDI and 0.01 part of TBT are placed, cooled to 30 ° C., and then 9 parts of HEMA is added. (0.07 mol) was added dropwise over 2 hours. Meanwhile, the reaction temperature was maintained at 40 to 50 ° C. The reaction solution was put into 963 parts (0.14 mol) of polyol (a-1) previously placed in a 1 L four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel. Stirred at ~ 90 ° C for 4 hours. After confirming that there was no unreacted isocyanate group in the infrared absorption spectrum, a reactive dispersant (D1-1) was obtained.
The hydroxyl value of (D1-1) was 20, the viscosity was 20,000 mPa · s / 25 ° C., and the ratio of the number of unsaturated groups / the number of nitrogen-containing bonds was 0.22.

<Production Example 2> Production of reactive dispersant (D1) -2
Reactive dispersant (D1-2) was prepared in the same manner as in Production Example 1 except that 9 parts of HEMA was replaced with 8 parts (0.07 mol) of HEA and 963 parts of polyol (a-1) was replaced with 964 parts (0.14 mol). ) Got.
The hydroxyl value of (D1-2) was 20, the viscosity was 19,500 mPa · s / 25 ° C., and the ratio of the number of unsaturated groups / the number of nitrogen-containing bonds was 0.22.

The compositions, symbols, etc. of the raw materials used in the following Examples and Comparative Examples are as follows.
(5) Polyol (A)
G50: a polyol having a number average molecular weight (hereinafter referred to as Mn) of 3,000 and a hydroxyl value of 56 obtained by adding 50 mol of PO to glycerin, and a viscosity of 500 mPa · s (25 ° C.).
Polyol A11-1: A polyol having an EO content of 15% and a hydroxyl value of 37.5 obtained by adding PO to glycerin on average of 64 mol and then adding EO on average of 15 mol.
Polyol A11-2: A polyol having an EO content of 12% and a hydroxyl value of 32 obtained by adding 104 mol of PO on average to pentaerythritol and then adding 19 mol of EO on average.
Polyol A11-3: A polyol having an EO content of 14% and a hydroxyl value of 28 obtained by adding 118 mol of PO on average to pentaerythritol and then adding 25 mol of EO on average.
Polyol A11-4: A polyol having an EO content of 18% and a hydroxyl value of 37.5 obtained by adding 83 mol of PO on average to pentaerythritol and then adding 24 mol of EO on average.

Polyol A12-1: a polyol having an EO content of 70% and a hydroxyl value of 24, obtained by randomly adding 35 mol of PO and 111 mol of EO to glycerin on average.
Polyol A12-2: A polyol having an EO content of 70% and a hydroxyl value of 112 obtained by randomly adding 6 mol of PO and 24 mol of EO to glycerin on average.
(6) Ethylenically unsaturated compound (b2)
AN: Acrylonitrile St: Styrene

(7) Dispersant (D)
SAN: acrylonitrile / styrene = 80/20 mass% copolymer (Mn = 5,000)
GMAP: glycidyl methacrylate equimolar addition product of polypropylene glycol (Mn = 3,000) Reactive dispersant (D1-1): prepared in Production Example 1 Reactive dispersant (D1-2): prepared in Production Example 2 (8) Polymerization initiator AVN: 2,2'-azobis (2,4-dimethylvaleronitrile)
(9) Organic polyisocyanate TDI-80: Coronate T-80 [manufactured by Nippon Polyurethane Industry Co., Ltd.]
TM-20: CE-729 [TDI / polymeric MDI = 80/20% by mass; manufactured by Nippon Polyurethane Co., Ltd.]
(10) Catalyst Catalyst A: Neostan U-28 (stannous octoate) [Nitto Kasei Co., Ltd.]
Catalyst B: DABCO (triethylenediamine) [Nippon Emulsifier Co., Ltd.]
Catalyst C: TEDAL-33 [triethylenediamine / dipropylene glycol = 33/67% by mass solution; manufactured by Tosoh Corporation]
Catalyst D: TOYOCAT ET [bis-2-dimethylaminoethyl ether / dipropylene glycol = 33/67% by mass solution: manufactured by Tosoh Corporation]
(11) Foam stabilizer F-242T: polyether siloxane polymer [manufactured by Shin-Etsu Chemical Co., Ltd.]
SZ-1311: polyether siloxane polymer [manufactured by Nippon Unicar Co., Ltd.]
L-5309: polyether siloxane polymer [manufactured by Nippon Unicar Co., Ltd.]

The number average molecular weight, degree of unsaturation, viscosity, polyol-soluble polymer, dispersion stability, and polymer particle diameter were measured as follows.
<Mn>
Model: HLC-8120GPC (Liquid chromatog made by Tosoh Corporation)
Raffy)
Column: TSK gel Super H4000
+ TSK gel Super H3000
+ TSK gel Super H2000
(All manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI (Refractive Index)
Solvent: tetrahydrofuran Flow rate: 0.6 ml / min Sample concentration: 0.25% by mass
Injection volume: 10 μl
Standard: Polystyrene
(Tosoh Corporation; TSK STANDARD
POLYSTYRENE)

<Unsaturation>
Measured according to the measurement method specified in JIS K-1557.
<Viscosity>
Model: BL viscometer (manufactured by TOKIMEC)
Measurement temperature: 25 ° C
Rotor No: No3 or No4
Number of rotations: Based on the measured viscosity, the viscosity V (mPa · s) is based on the number of rotations described in the description of the equation (1).

<Polyol-soluble polymer>
According to the method described above. However, the following preparative liquid chromatograph was used.
Model: LC-09 (manufactured by Nippon Kagaku Kogyo Co., Ltd.)
Column: JAIGEL-1H
+ JAIGEL-2H
+ JAIGEL-3H
(All manufactured by Nippon Kagaku Kogyo Co., Ltd.)
Column temperature: 40 ° C
Detector: RI
Solvent: chloroform Flow rate: 2.5 ml / min Sample concentration: 0.25% by mass
Injection volume: 4 ml x 12 times

<Dispersion stability [1]>
The polymer polyol composition contained in a 140 ml glass sealed container (sample bottle) is left in a thermostat at 50 ° C. for 30 days. After standing, the dispersion stability was visually checked.
Evaluation criteria ○ There was no sediment and it was in a uniformly dispersed state.
△ There was a sediment, and after the sample bottle was turned down 5 times, it was uniformly redispersed.
X: There was a precipitate, and the sample bottle was not redispersed after turning over five times.
<Dispersion stability [2]>
The polymer polyol composition contained in a 140 ml glass sealed container (sample bottle) is left in a constant temperature bath at 70 ° C. for 30 days. After standing, the dispersion stability was visually checked.
Evaluation criteria ◎ There was no sediment and the particles were in a uniformly dispersed state.
○ There was a sediment, and after the sample bottle was turned down 5 times, it was uniformly redispersed.
X: There was a precipitate, and the sample bottle was not redispersed after turning over five times.

<Polymer particle size>
The polymer polyol is diluted with the polyol A11 used so that the transmittance of the laser light becomes 70 to 90%, and a particle size distribution measuring device (laser diffraction / scattering type particle size distribution measuring device LA-700; manufactured by Horiba, Ltd.) Was measured. The particle diameter corresponding to 50% of the volume-based particle size distribution was defined as the polymer particle diameter (μm).

<Example 1> Production of polymer polyol composition-1
SAN: 10 parts and G50: 440 parts were charged into a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a pressure reducing device, a Dimroth condenser, a nitrogen inlet and an outlet, and after nitrogen replacement, nitrogen was replaced. The temperature was raised to 130 ° C. while stirring under an atmosphere (until the polymerization was completed). Next, a raw material in which 250 mol of allyl alcohol propylene oxide adduct (Mn = 186, SP = 10.2): 250 parts of AN: 150 parts, St: 100 parts, and G50: 50 parts in advance And AVN: the raw materials obtained by mixing 1 part were continuously dropped simultaneously over 1 hour using a dropping pump, respectively, and polymerized at 130 ° C. for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-1) having a polymer particle content of 50% and a viscosity of 4000 mPa · s (25 ° C.).

<Example 2> Production of polymer polyol composition-2
Into the same four-necked flask as in Example 1, 10 parts of SAN and 440 parts of G50 were charged, and after replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the end of polymerization). Next, a raw material obtained by previously mixing a compound having an acetoacetyl group of the following formula [6] (Mn = 215, SP = 11.5): 200 parts, AN: 150 parts, St: 150 parts, and G50: A raw material obtained by mixing 50 parts and AVN: 1 part was dropped simultaneously continuously over 1 hour using a dropping pump, and polymerized at 130 ° C. for 2 hours. Further, the unreacted monomer was stripped under reduced pressure to obtain a polymer polyol composition (F-2) having a polymer particle content of 50% and a viscosity of 4000 mPa · s (25 ° C.).
CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ OCOCH ₂ COCH ₃ [6]

<Example 3> Production of polymer polyol composition-3
Into the same four-necked flask as in Example 1, 10 parts of SAN and 440 parts of G50 were charged, and after replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the end of polymerization). Next, a raw material obtained by previously mixing 50 parts of a compound having a ring-opened lactone chain represented by the following formula [7] (Mn = 300, SP = 10.4), 200 parts of AN, and 250 parts of St: : 50 parts and AVN: 1 part were mixed at the same time and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-3) having a polymer particle content of 50% and a viscosity of 4,200 mPa · s (25 ° C.).
CH ₂ ＣＨCHCO [O (CH ₂ ) ₅ CO] ₂ OH [7]

Example 4 Production of Polymer Polyol Composition-4
Into the same four-necked flask as in Example 1, 10 parts of SAN and 440 parts of G50 were charged, and after replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the end of polymerization). Next, a raw material obtained by previously mixing a compound having a succinic acid residue of the following formula [8] (Mn = 230, SP = 11.2): 180 parts, AN: 160 parts, St: 160 parts, and G50 : 50 parts and AVN: 1 part were mixed at the same time and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-4) having a polymer particle content of 50% and a viscosity of 4900 mPa · s (25 ° C.).
CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ OCOCH ₂ CH ₂ COOH [8]

<Example 5> Production of polymer polyol composition-5
Into the same four-necked flask as in Example 1, 10 parts of SAN and 440 parts of G50 were charged, and after replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the end of polymerization). Next, a raw material obtained by previously mixing a compound having a phthalic acid residue of the following formula [9] (Mn = 336, SP = 12.0): 250 parts, AN: 150 parts, St: 100 parts, and G50 : 50 parts and AVN: 1 part were mixed at the same time and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-5) having a polymer particle content of 50% and a viscosity of 5300 mPa · s (25 ° C.).
CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ OCO (Ph) COOCH ₂ CH (OH) CH ₃
[However, (Ph) is an orthophenylene group] [9]

<Example 6> Production of polymer polyol composition-6
Polymer polyol having a polymer particle content of 50% and a viscosity of 3800 mPa · s (25 ° C.) in the same manner as in Example 1 except that SAN: 10 parts of the dispersant is changed to 10 parts of the reactive dispersant (D1-1). A composition (F-6) was obtained.

<Example 7> Production of polymer polyol composition-7
Polymer polyol having a polymer particle content of 50% and a viscosity of 3900 mPa · s (25 ° C.) in the same manner as in Example 1, except that SAN: 10 parts of the dispersant is replaced by 10 parts of the reactive dispersant (D1-2). A composition (F-7) was obtained.

Example 8 Production of Polymer Polyol Composition-8
Into the same four-neck flask as in Example 1, 10 parts of the reactive dispersant (D1-1), 440 parts of G50 and 80 parts of xylene were charged, and after purging with nitrogen, the mixture was stirred under a nitrogen atmosphere (until the polymerization was completed). While heating, the temperature was raised to 130 ° C. Next, a raw material in which 250 mol of allyl alcohol propylene oxide adduct (Mn = 186, SP = 10.2): 250 parts of AN: 150 parts, St: 100 parts, and G50: 50 parts in advance And AVN: the raw materials obtained by mixing 1 part were continuously dropped simultaneously over 1 hour using a dropping pump, respectively, and polymerized at 130 ° C. for 2 hours. Water: 20 parts was added to the reaction product, and then xylene and unreacted monomers were removed by vacuum stripping at 10 mmHg at 130 ° C. for 3 hours, and a polymer having a polymer particle content of 50% and a viscosity of 3100 mPa · s (25 ° C.) A polyol composition (F-8) was obtained.

<Examples 9 to 13> Production of polymer polyol composition-9 to 13
According to the composition shown in Table 3, 25% equivalent of polyol was put into a 1 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet. Then, the mixture was heated to 125 ° C. with stirring, and then the raw material liquid (remaining raw material blended liquid) was continuously dropped by a dropping pump over 4 hours, and the unreacted monomer was stripped under reduced pressure to obtain the polymer of the present invention. Polyol compositions (F-9) to (F-13) were synthesized. Table 3 shows their properties and the like.

Comparative Example 1 Production of Comparative Polymer Polyol Composition-1
50:50 parts of G was placed in the same four-necked flask as in Example 1, and heated to 125 ° C. with stirring. Next, a raw material in which 450 parts of St, 300 parts of ACN, 20 parts of GMAP, 680 parts of G50 and 4 parts of AVN were previously mixed was continuously dropped by a dropping pump over 4 hours, and polymerized. Further, unreacted monomers were stripped under reduced pressure. A comparative polymer polyol composition (R-1) having a polymer particle content of 50% and a viscosity of 20,000 mPa · s (25 ° C.) was obtained.

Comparative Example 2 Production of Comparative Polymer Polyol Composition-2
Using the same apparatus and method as in Comparative Example 1, polymer particle content using 150 parts of G50 and 280 parts of St, 120 parts of AN, 8 parts of GMAP, 442 parts of G50 and 1.6 parts of AVN A comparative polymer polyol composition (R-2) having a viscosity of 5540 mPa · s (25 ° C.) at 40% was obtained.

Comparative Example 3 Production of Comparative Polymer Polyol Composition-3
Polymer particle content using the same apparatus and method as in Comparative Example 1, using 175 parts of G50 and 210 parts of St, 90 parts of AN, 6 parts of GMAP, 519 parts of G50 and 1.2 parts of AVN. A comparative polymer polyol composition (R-3) having 30% and a viscosity of 2000 mPa · s (25 ° C.) was obtained.

<Comparative Examples 4 to 5> Production of Comparative Polymer Polyol Compositions-4 to 5
According to the composition shown in Table 3, 25% equivalent of polyol was put into a 1 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet. Then, the mixture was 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, and the unreacted monomer was further stripped under reduced pressure to obtain a comparative polymer polyol. Compositions (R-4) to (R-5) were synthesized. Table 3 shows their properties and the like.

<Examples 1 to 8 and Comparative Examples 1 to 3> Production of Polyurethane Foam The polymer polyol compositions (F-1 to F-8) of the present invention obtained from Examples 1 to 8 and Comparative Examples 1 to 3 and Using the comparative polymer polyol compositions (R-1 to R-3), polyurethane foams were produced at the compounding ratios shown in Tables 1 and 2 by the following foaming formulation. Tables 1 and 2 show the evaluation results of these foam properties. The foaming formulation is as follows.
[1] The temperature of each of the polymer polyol composition and the organic polyisocyanate is adjusted to 25 ± 2 ° C.
[2] A polymer polyol composition, a foam stabilizer, water, and a catalyst are placed in a stainless beaker having a capacity of 1 liter in this order, and stirred and mixed at room temperature (25 ± 2 ° C.). Using a homodisper (manufactured by Tokushu Kika Co., Ltd., stirring condition: 2000 rpm × 6 seconds), the mixture was stirred and foamed.
[3] After the stirring was stopped, the contents were put into a wooden box of 25 × 25 × 10 cm to obtain a polyurethane foam.

<Examples 9 to 13 and Comparative Examples 4 to 5> Production of polyurethane foam Using a comparative polymer polyol composition obtained by the formulation shown in Table 3 and some of the polymer polyol compositions of the present invention, Table 3 was used. The raw materials were stirred and mixed at 25 ± 2 ° C. according to the foaming formulation described in 1 above, and the mold temperature was 60 ° C. and the curing time was 6 minutes to produce a polyurethane resin. Table 4 shows the evaluation results of these foam physical properties.

The methods for evaluating foam properties in Tables 1, 2 and 4 are as follows.
Density (kg / m ³ ): 25% ILD (hardness) according to JIS K6400-1997 [Item 5] (kgf / 314 cm ² )
: Tensile strength (kgf / cm ² ) in accordance with JIS K 6382-1995 [Item 5.3]: Tear strength (kgf / cm) in accordance with JIS K 6301-1995 [Item 3]: In accordance with JIS K6301-1995 [Item 9] Elongation at break (%): compliant with JIS K6301-1995 [item 3] Rebound resilience (%): compliant with JIS K6400-1997 [item 7] Air permeability (ft ³ / min): Dow flow meter method [AMSCOR] Company)
(Test piece 5cm × 5cm × 2.5cm)
Compression set (%): conforms to JIS K6382-1995 [item 5.5] Wet heat compression set (%): conforms to JIS K6382-1995 [item 5.5] In addition, density is usually used as a physical property of urethane foam. Is preferably in the range of 15 to 50, and 25% ILD, tensile strength, tear strength, cut elongation, rebound resilience and air permeability are preferably as large as possible. The smaller the numerical values of the compression set and the wet heat compression set, the more preferable.

As is clear from Tables 1 and 2, the polymer polyol compositions of Examples 1 to 8 have a lower viscosity than the polymer polyol composition of Comparative Example 1, and furthermore have a foam property in the case of a polyurethane foam, particularly , 25% ILD (hardness), breathability and compression set. Further, the tear strength, tensile strength, elongation at break, and rebound resilience were equal or higher. In addition, since the polymer polyol compositions of Comparative Examples 2 and 3 have lower concentrations of polymer particles than the polymer polyol compositions of Examples 1 to 8 and the comparative polymer polyol composition of Comparative Example 1, the viscosity is low. In the case of a foam, the properties of the foam, particularly, the 25% ILD (hardness) are remarkably inferior. In general, the higher the concentration of the polymer particles, the lower the tensile strength, the elongation at break, the rebound resilience, and the air permeability, and the compression set tends to be higher, but the polyurethane using the polymer polyol composition of the present invention tends to be higher. The foams (Examples 1 to 8) show comparable or higher foam properties as compared to Comparative Example 1 having the same polymer particle concentration.
Furthermore, as is clear from Table 4, the polymer polyol compositions of Examples 9 to 13 have lower viscosities than the polymer polyol compositions of Comparative Examples 4 to 5, and furthermore have a foam property in the case of a polyurethane foam. In particular, the wet heat compression set is excellent.

  Because of the above effects, the polyurethane resin produced by using the polymer polyol composition of the present invention is extremely suitable as a polyurethane foam for applications such as interior parts of automobiles and interior preparation of furniture and the like.

Claims (9)

A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein (B) is 100 parts by mass of (A) in the dispersion medium. A polymer polyol composition formed by polymerizing an ethylenically unsaturated compound (b) in the presence of 0.5 to 50 parts by mass of the following reactive dispersant (D1).
Reactive dispersant (D1): a substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one ethylenically unsaturated group are bound via a polyisocyanate (f). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol. A dispersion medium comprising a polyol (A) or (A) and a diluent (C); and polymer particles (B) dispersed in the dispersion medium, wherein (B) comprises the following reactive dispersant ( A polymer polyol composition formed by polymerizing the ethylenically unsaturated compound (b) in the presence of D11).
Reactive dispersant (D11): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). (D11) a dispersant comprising a nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4. . The content of (B) is 35 to 75% by mass based on the mass of the polymer polyol composition, and the amount of the soluble polymer (P) dissolved in (A) is 5% by mass based on the mass of (A). % Of the polymer polyol composition according to claim 1. The content of (B) is 35 to 75% by mass based on the mass of the polymer polyol composition, and the viscosity V (mPa · s) measured at 25 ° C. by a Brookfield viscometer is within the range of the following formula (1). The polymer polyol composition according to any one of claims 1 to 3, wherein
V ≦ (Va−Va × C / 10) ＾ [e ＾ x] (1)
However, x = 0.0010354 × Bp ＾ 1.5
Va: Viscosity (mPa · s) of (A) at 25 ° C. measured by a Brookfield viscometer.
C: Content (% by mass) of (C) in the polymer polyol composition
Bp: content (% by mass) of (B) in the polymer polyol composition
＾: Power.
e: base of natural logarithm. 3. The polymer polyol composition according to claim 1, wherein (A) comprises the following (A11) and, if necessary, (A12), and the mass ratio of (A11) to (A12) is from 100: 0 to 50:50.
Polyol (A11): The average number of functional groups is 2.5 to 4, the hydroxyl value is 20 to 40 (mgKOH / g), the content of oxyethylene units is 10 to 30% by mass, and the terminal oxyethylene A polyoxyethylene polyoxypropylene polyol having a unit content of 10 to 25% by mass.
Polyol (A12): Polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 2 to 6, a hydroxyl value of 15 to 130 (mgKOH / g), and an oxyethylene unit content of 50 to 80% by mass. . In the method for producing a polymer polyol composition in which an ethylenically unsaturated compound (b) is polymerized in a polyol (A) in the presence of a dispersant (D), in the presence or absence of a diluent (C), The method according to claim 1, wherein the polymer polyol composition according to claim 1 is obtained by using the following reactive dispersant (D1) as the agent (D).
Reactive dispersant (D1): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol. In the method for producing a polymer polyol composition in which an ethylenically unsaturated compound (b) is polymerized in a polyol (A) in the presence of a dispersant (D), in the presence or absence of a diluent (C), A method comprising using the following reactive dispersant (D11) as the agent (D) to obtain the polymer polyol composition according to claim 2.
Reactive dispersant (D11): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). (D11) a dispersant comprising a nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4. . 8. The method according to claim 6, wherein the diluent (C) is composed of an aromatic hydrocarbon solvent. A method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component and a polyisocyanate component in the presence or absence of a foaming agent, wherein at least a part of the polyol component according to any one of claims 1 to 5. A method for producing a polyurethane resin, comprising using a polymer polyol composition.