WO2001009242A1 - Polymer polyol composition, process for producing the same, and process for producing polyurethane resin - Google Patents

Abstract

A polymer polyol composition (I) comprising a polyol (A) and, dispersed in (A), polymer particles (B) formed by polymerizing an ethylenically unsaturated compound (b) in a polyol, wherein the content of (B) is 35 to 75 wt.% based on (I) and the amount of a soluble polymer (P) which is dissolving in (A) is up to 5 wt.% based on (A); and a process for producing a foamed or unfoamed polyurethane resin which comprises reacting a polyol ingredient with a polyisocyanate ingredient in the presence or absence of a blowing agent, wherein the polymer polyol composition is used as at least part of the polyol ingredient. The polymer polyol composition has a low viscosity and excellent dispersion stability even when having a heightened polymer particle concentration. It is useful for efficiently producing a polyurethane resin excellent in 25% ILD (hardness) and compression set or a foam thereof.

Description

 Description Polymer polyol composition, method for producing the same, and method for producing a polyurethane resin

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

 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. .

 For the purpose of producing a polymer polyol that gives a higher quality polyurethane having higher hardness and elastic modulus, the content of polymer particles in the polymer polyol is further increased. A method in which a vinyl monomer is polymerized in the presence of a modified polyol having a high molecular weight by reacting a part thereof with a coupling agent (silicon-containing compound, tetraxyalkoxy orthoformate, trialkoxyalkane, dialkoxyalkane, etc.). (For example, International Publication WO85 / 04891), a method of polymerizing a vinyl monomer in the presence of a macromer containing a urethane bond (for example, Japanese Patent Application Laid-Open No. 61-15991) No. 19).

However, the dispersion stability of the obtained polymer polyol composition is poor. Polymer polyol composition with good dispersion stability even when polymer particles content is high due to problems such as poor mixing with polyurethane resin during molding of polyurethane resin and difficulty in handling. Was difficult to obtain.

 The present inventors have conducted intensive studies to solve the above problems, and as a result, by reducing the oligomer content to a specific amount or less, a high-quality polyurethane is obtained, and a low-viscosity polymer polyol composition is obtained. The present invention was found. Further, they have found that a similar polymer polyol composition can be obtained by mechanically dispersing or pulverizing a polymer polyol obtained by polymerizing a monomer in the presence of a specific dispersant, and reached the present invention. An object of the present invention is to provide a polymer polyol having a low viscosity and extremely excellent dispersion stability even when the concentration of the polymer particles is increased, and a method for producing the same. The present invention also relates to a method for producing a polyurethane resin or a foam thereof using the polymer polyol composition, which has a good work efficiency, a 25% ILD (hardness) and a compression set. It is an object of the present invention to provide a method for producing a polyurethane resin or a foamed body thereof excellent in the above. Summary of the Invention

 That is, the present invention is as follows.

 [First invention] It comprises a polyol (A) and polymer particles (B) dispersed in (A), wherein (B) is formed by polymerizing an ethylenically unsaturated compound (b) in a polyol. In the polymer polyol composition (I), the content of (B) is 35 to 75% by mass based on the mass of (I), and the soluble polymer (P) dissolved in (A) ) Is 5% by mass or less based on the mass of (A).

[Second invention] Consisting of polyol (A) or (A) and diluent (C) And a polymer particle (B) dispersed in the dispersion medium.

In the polymer polyol composition (I) in which (B) is formed by polymerizing an ethylenically unsaturated compound (b) in a polyol, the content of (B) is 35% based on the mass of (I). A polymer polyol composition having a viscosity V (mPa · s) measured by a Brookfield viscometer at 25 of (I) in the range of the following formula (1).

 V≤ (V a-V a X C / 10) [e 'x] (1) where x = 0.0010354X B p — 1.5

 V a: viscosity (mP a · s) of (A) measured at 25 ° C by a Brookfield viscometer.

 C: Content of (C) in (I) (% by mass)

 B p: Content of (B) in (I) (% by mass)

 ": Indicates a power.

 e: base of natural logarithm.

 [Third invention] Polyol (A) and polymer particles (B) dispersed in (A), wherein (B) is an ethylenically unsaturated compound in the polyol.

In the polymer polyol composition (II) formed by polymerizing (b), in (A), in the presence of a dispersant (D), in the presence or absence of a diluent (C), A polymer polyol composition obtained by polymerizing (b) containing 5% by mass or more of an ethylenically unsaturated compound (b 1) having a number average molecular weight of 500 or more.

[Fourth Invention] In a polymer polyol composition comprising a polyol (A) and polymer particles (B) dispersed in (A), (B) is a polymer (A) in a dispersion medium comprising (A). ) Is a polymerizable product of ethylenically unsaturated compound (b) in the presence of dispersant (D ') having a solubility parameter of SP d with a difference of 0.8 or less from SP a Polymer particles A polymer polyol composition (111) which is a polymer particle obtained by further mechanically dispersing or pulverizing a polymer.

 [Fifth invention] 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 Z or a diluent (C). In the production method, the (b) containing at least 5 masses of the ethylenically unsaturated compound (b 1) having a number average molecular weight of 500 or more is used to produce the first, second or third invention. A method for producing a polymer polyol composition, comprising obtaining any of the polymer polyol compositions (I) and (II).

 [Sixth invention] In a method for producing a polymer polyol composition comprising a polyol (A) and polymer particles (B) dispersed in (A), an ethylenically unsaturated compound (b) The polymer particles obtained by polymerizing the polymer-polymer particles (B) separated from the polyol composition are mixed in (A) which does not contain more than 5% by mass of a soluble polymer based on the mass of (A). A process for producing the polymer polyol composition (I) according to the first or second invention, which comprises mechanically dispersing.

 [Seventh invention] A dispersant (D ') having a solubility parameter of 1 SPd and a difference of 0.8 or less from the solubility parameter of SP (A) in a dispersion medium comprising the polyol (A). The polymer particles in the polymer polyol obtained by polymerizing the ethylenically unsaturated compound (b) in the presence thereof, and further mechanically dispersing or pulverizing the polymer particles in the polymer polyol composition (III) of the fourth invention. Production method.

[Eighth 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, the method comprises the steps of: The use of the polymer-polyol composition of any of the inventions to the fourth invention A method for producing a polyurethane resin. Detailed Disclosure of the Invention

 In the first invention of the present invention, the content of the polymer particles (B) dispersed in (A) in the polymer polyol composition (I) is usually 35 to 75% by mass, preferably 45 to 75% by mass. It is 75% by mass. If the content of (B) is less than 35% by mass, sufficient foam compression hardness cannot be obtained when a polyurethane foam is produced. On the other hand, if it exceeds 75% by mass, the polymer particles will aggregate and settle, making handling difficult.

 In the first invention, the amount of the soluble polymer (P) dissolved in the polyol (A) in (I) must be 5% by mass or less based on the mass of (A). It is preferably at most 3% by mass. If the amount of (P) is more than 5% by mass, the viscosity of the polymer-polyol composition becomes so high that handling becomes difficult, and the hardness of the foamed polyurethane foam becomes low.

 Here, the soluble polymer (P) dissolved in the polyol (A) is defined as the polymer particles (B) and (A) (a small amount of low polymer particles) insoluble in (A) from the polymer polyol composition (I). (Including molecular weight by-products) and is usually a compound with a higher molecular weight than the polyol (A).

 The amount of the soluble polymer (P) is measured by the following method.

To 5 g of (I), add 2 Og of methanol, place in a 100 cc stainless steel tube, and centrifuge at 180 ° C for 60 minutes at 20 ° C to aggregate (B). To obtain a clear supernatant solution. After removing methanol from the solution by a vacuum dryer, preparative liquid chromatography was used to determine the polyol (A) (including a small amount of low molecular weight by-products) and the polymer (P) soluble in (A) (molecular weight 4000 or more, usually chromatography A peak appears on the higher molecular weight side than the peak of (A) in-. ] And obtain from the mass ratio. The weight-average molecular weight of (P) (based on gel permeation chromatography, hereinafter abbreviated as GPC) is usually from 600,000 to 300,000, but may further include high molecular weight ones. If the polymer (P) cannot be separated from the polyol (A) by preparative liquid chromatography (when the molecular weights overlap), centrifugation is performed as above to aggregate (B), and a clear supernatant solution is obtained. . After methanol is removed from this solution by a vacuum drier, getyl ether is injected, and the precipitate is separated by filtration and dried, whereby the soluble polymer (P) can be separated from (A).

 In the second invention of the present invention, the content of the polymer particles (B) in the polymer polyol composition (I) is usually 35 to 75% by mass, preferably 45 to 75% by mass. If the content of (B) is less than 35% by mass, sufficient foam compression hardness cannot be obtained when polyurethane foam is produced. If it exceeds 75% by mass, the polymer particles will aggregate and settle, making handling difficult.

 In the second invention, the polymer polyol composition (I) generally has a viscosity V (mP a · s) measured at 25 ° C. by a Brookfield viscometer within the range of the following formula (1). Preferably, the following formula (2) and

 (3) A polymer polyol composition falling within the range satisfying both. V≤ (V a -V a X C / 10) "[e" x] (1)

 V≤ (V a -V a X C / 10) "[e — y] (2)

 V≥0.5X (V a-V a X C / 10) ~ (e "y) (3)

 Where x = 0.0010354X B p ~ 1.5

 y = 0.0009514X B p "1.5

V a: viscosity of (A) measured at 25 ° C by Brookfield viscometer Degree (mP a S)

 Content of (C) in C (I): (% by mass)

 Content of (B) in B p (I): (% by mass)

 Indicates a power.

 e Natural log base.

 However, the measurement of V and Va is based on the following conditions

 1500mPa's or less No.3, 60rpm

 1500 ~ 3000mPa-s Mouth one evening NO.3, 30rpm

 3000—8000mPa-s 3, 12rpm

 8000—16000mPa-s rotor NO.3, 6rpm

 16000〜 40000mPa-s NO.4, 12rpm

 40000—100000mPa-s rotor NO.4, 6rpm By satisfying the range of the above formula (1), the polymer polyol composition (I) has a good mixability with other raw materials, and has good handleability. It can be a composition.

 In the second invention, the viscosity of the polymer polyol composition may be further reduced by using a diluent (C) if necessary. (C) includes olefins such as hexene, octene, and decene; internal olefins having 5 to 30 carbon atoms; low-viscosity (less than 100 mPa · s / 25) flame retardants, for example, tris (chloroethyl) phosphate And a solvent such as toluene and xylene; and a solvent such as aromatic solvent such as toluene and xylene.

 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.

 Polymer polyol compositions of the first and second or second inventions

Methods for obtaining (I) include, for example, the following (i) and (ii): It is.

 (i) [the fifth invention] In the polyol (A), an ethylenically unsaturated compound (b) is polymerized in the presence or absence of a dispersant (D) and Z or a diluent (C), In producing the polymer polyol composition, an ethylenically unsaturated compound (bl) having a number average molecular weight of 500 or more is used in an amount of 5% by mass or more in (b).

 (ii) [Sixth invention] The polymer particles (B) separated from the polymer polyol composition obtained by polymerizing (b) in a polyol are used in an amount of more than 5% by mass based on the mass of (A). A polymer polyol composition comprising a polyol (A) and polymer particles (B) dispersed in (A) is produced by mechanically dispersing in (A) which does not contain a soluble polymer. Of these, method (i) is preferred.

 A third invention of the present invention is the polymer polyol composition (II) obtained by using the dispersant (D) as an essential component in the method of the fifth invention. The content of the soluble polymer (P) is preferably 5% by mass or less based on the mass of (A), but may be 10% by mass or less, which is used in the first to third inventions. As the polyol (A), known polyols usually used for producing a polymer polyol can be used. For example, a structure in which an alkylene oxide is added to a compound containing at least 2 (preferably 2 to 8) active hydrogens (polyhydric alcohol, polyphenol, amines, polycarboxylic acid, phosphoric acid, etc.) The compound (A 1) and a mixture thereof are mentioned.

 Of these, preferred are compounds obtained by adding an alkylene oxide to a polyhydric alcohol.

Polyhydric alcohols include dihydric alcohols having 2 to 12 carbon atoms (eg, ethylene glycol, diethylene glycol, propylene glycol, 1,3_ or 1,4-butanediol, 1,6-hexanediol, neopentyldaricol and cyclohexanediol), trihydric alcohols having 3 to 12 carbon atoms (e.g., glycerin, trimethylolpropane. Trimethylolethane, hexanetriol and triethanolamine); alcohols having 4 to 8 or more carbon atoms having 5 to 18 carbon atoms (for example, pen erythritol, methyl darcoside, sorbitan, diglycerin, dipentaerythritol, Sorbitol, mannitol, glucose, mannose, fructoses and sucrose).

 Examples of polyvalent phenols include monocyclic polyvalent phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenol A, bisphenol? And bisphenols such as bisphenolsulfone; and condensates (nopolak) of phenol and formaldehyde.

 As amines, ammonia; As aliphatic amines, alkanolamines having 2 to 18 carbon atoms (for example, monoethanolamine, genoaluminamine, isopropanolamine, and aminoethylethanolamine); 20 alkylamines (for example, n-butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), polyalkylenepolyamines (alkylene group From dialkylenetriamines having 2 to 6 carbon atoms to hexaalkylenehepamines, for example, diethylenetriamine and triethylenetetramine).

Also, aromatic mono- or polyamines having 6 to 20 carbon atoms (for example, aniline, phenylenediamine, tolylene diamine, xylylene diamine, methylene dianiline and diphenyl ether diamine); Alicyclic amines (isophorone diamine, cyclohexylene diamine Amine and dicyclohexylmethanediamine); and C4-C15 complex cyclic amines (eg, aminoethylpiperazine). Examples of polycarboxylic acids include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (such as succinic acid, adipic acid, sebacic acid, glutaric acid, and azelaic acid), and aromatic polycarboxylic acids having 8 to 18 carbon atoms ( Terephthalic acid, isophthalic acid, etc.), and mixtures of two or more of these. Examples of the alkylene oxide to be added to the active hydrogen-containing compound include those having 2 to 8 carbon atoms, such as ethylene oxide (hereinafter abbreviated as E〇), propylene oxide (hereinafter abbreviated as P〇). ), Butylene oxide (hereinafter abbreviated as BO), styrene oxide (hereinafter abbreviated as SO), and combinations of two or more of these (block addition and Z or random addition). Can be 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 P〇 to the active hydrogen-containing compound, those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO) in the following manner, or compounds obtained by adding these compounds. And an esterified product thereof with polycarboxylic acid or phosphoric acid.

 ① Blocks added in the order of P 0 _ A O (tipped)

 ② Block added in the order of P O— A O— P O— A〇 (balanced)

 ③ A O— Blocks added in the order of P〇_A〇

 ④ P O— A O— Block added in the order of P O (active secondary—)

 ラ ン ダ ム Random adduct with mixed addition of P O and A O

も の Random addition or block addition in the order described in U.S. Pat.No. 4,226,756 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 usage ratio of (A l) / (A2) is usually 100 to 0 Z 80 by mass ratio.

 Examples of other polyols (A2) include high molecular weight polyols such as polyester polyols and modified polyols, and mixtures thereof. Examples of the polyester polyol include the above-mentioned polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl alcohol such as neopentyl alcohol, and the like) A mixture of a trivalent or higher alcohol such as glycerin and trimethylolpropane) and the above-mentioned polycarboxylic acid or an anhydride thereof, or an ester-forming derivative such as a lower ester thereof (eg, adipic acid, sebacic acid, maleic anhydride) Condensation reaction product with acid, phthalic anhydride, dimethyl terephthalate, etc.); addition product of its alkylene oxide (EO, PO, etc.); Ring-opening polymerization of lactone (ε-force prolactone, etc.) And the like.

 Examples of the modified polyol include polygen polyols such as polybutadiene polyol; 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 high molecular polyols usually have 2 to 8, preferably 3 to 8, hydroxyl groups and usually have a hydroxyl equivalent weight of 200 to 4,000, preferably 400 to 3,000.

The number average molecular weight of the polyol (Α) (according to GPC; the same applies to the following number average molecular weights) is usually 500 or more, preferably 500 to 20,000, and particularly preferably 1,200 to 15. , 000, most preferably 2, 0 0 to 9 and 0 0 0. When the number average molecular weight is at least 50,000, the polyurethane foam is less likely to be brittle, which is preferable. When the viscosity is less than 200,000, the viscosity becomes low, which is preferable in view of the handleability of the polymer polyol. In the sixth invention, the same polyol as the above-mentioned polyol (A) can also be used as the polyol used when polymerizing (b) to obtain polymer particles (B). The polyol and (A) may be the same or different.

The dispersant (D) used in the third and fifth aspects of the present invention is not particularly limited, and a usual dispersant used in polymer polyols can be used. For example, (1) a macromer-type dispersant obtained by reacting a polyol such as a modified polyether polyol containing an ethylenically unsaturated group (see, for example, Japanese Patent Application Laid-Open No. 08-33508) with an ethylenically unsaturated compound; (2) Two or more polyol affinity segments with a solubility parameter difference of 1.0 or less from the polyol are used as side chains, and the difference in solubility parameter from the vinyl monomer to the polymer is 2.0 or less. A graft-type dispersant in which a polyol and an oligomer such as a graft-type polymer having a polymer-affinity segment as a main chain (for example, see Japanese Patent Application Laid-Open No. 05-09134) are used; Modified polyols obtained by reacting at least a part of the hydroxyl groups of a polyol with methylene dihalide and Z or ethylene dihalide to increase the molecular weight (for example, Japanese Patent Application Laid-Open No. 07-196649) And a vinyl-type oligomer having a weight-average molecular weight of 100 to 300, at least a part of which is soluble in a polyol; And oligomer-type dispersants such as dispersants using modified polyether polyols containing ethylenically unsaturated groups (see, for example, Japanese Patent Application Laid-Open No. 09-77968). Of these, those of type I and II are preferred. In each case, the number average molecule Preferably, the quantity (according to GPC) is between 1,000 and 100,000. The amount of (D) used is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0.1 to 3% by mass, based on the mass of (b).

 Polymer polyol composition of the first invention and Z or the second invention

(I) and the method (i) for obtaining the polymer polyol composition (II) of the third invention (i) In the fifth invention, the ethylenically unsaturated compound (b) has a number average molecular weight of 500 The above ethylenically unsaturated compound (b 1) and the ethylenically unsaturated compound (b 2) having a number average molecular weight of less than 500, which is generally used for producing a polymer polyol composition, can be used. Are aromatic hydrocarbon monomers (b2-l), unsaturated nitriles (b2-2), (meth) acrylates (b2-3), and other ethylenically unsaturated compounds (b 2-4), and mixtures of two or more of these.

 The number average molecular weight of the ethylenically unsaturated compound (bl) is usually at least 500, preferably at least 550, particularly preferably from 800 to 100,000, most preferably from 1,000 to 10,00. , 000. By setting the number average molecular weight to 500 or more, the amount of the polyol-soluble oligomer in the polymer polyol produced using these can be reduced, which is preferable.

 The number of double bonds in the ethylenically unsaturated compound (bl) should be at least one on average. The number is preferably 1 to 500, and more preferably 1 to 70. By setting the number of double bonds to one or more on average, the soluble component of the polyol can be reduced, and an increase in the viscosity of the obtained polymer polyol can be prevented. In addition, it is possible to prevent a decrease in physical properties of the polyurethane resin produced by using these, which is preferable.

If the number of double bonds is 2 or more, it must be a non-conjugated double bond Is preferred.

 The molecular weight (X) per single double bond of (b 1) is usually 1200 or less, preferably 115 or less, and more preferably 100 to 150. When the molecular weight is not more than 1200, the effect of reducing the polyol-soluble oligomer in the polymer polyol produced by using them is large, which is preferable.

 Here, the molecular weight (X) per double bond of (bl) is defined by the following equation.

 X = 1 0 0 0 / N

 N: Degree of unsaturation of (b 1) measured by the measurement method specified in JISK-1 557

 The ethylenically unsaturated compound (bl) is preferably a compound having an ester bond, an amide bond, a urethane bond, a urea bond, a Z or imide bond or the like in the molecule. Of these, an ester bond, an amide bond and a Z or urethane bond are more preferred, and an ester bond is particularly preferred. Note that two or more kinds of the above bonds may be mixed in the same molecule. The ester bond can be formed by (1) the reaction of a carboxylic acid or acid anhydride with a hydroxyl group-containing compound or an alkylene oxide, or (2) the ring-opening reaction of lactone. Can be produced by the reaction of a product with an amino group-containing compound, or by the ① ring opening reaction of lactam, or ③ by the polycondensation reaction of an aminocarboxylic acid. An imide bond can be formed by the reaction of an acid with diamine to form a polyamic acid, followed by a dehydration reaction. The urethane bond or the urea bond can be formed by reacting an isocyanate compound with an active hydrogen-containing compound.

Examples of carboxylic acids that form ester bonds and amide bonds include unsaturated aliphatic monocarboxylic acids having 3 to 24 carbon atoms, such as acrylic acid, Methacrylic acid, oleic acid and linoleic acid; unsaturated aliphatic dicarboxylic acids having 4 to 24 carbon atoms, such as maleic acid, fumaric acid, itaconic acid and citraconic acid; saturated aliphatic polycarboxylic acids having 2 to 24 carbon atoms Carboxylic acids, for example, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, sebacic acid, hexanetricarboxylic acid and hexanetetracarboxylic acid; aromatic polycarboxylic acids having 8 to 24 carbon atoms, for example, isofuryl Acid and terephthalic acid; alicyclic dicarboxylic acids having 7 to 24 carbon atoms, for example, 1,4-cyclohexanedicarboxylic acid and tetrahydrofluoric acid; unsaturated carboxylic acid (co) polymer [number-average molecular weight 1, [0000]], for example, poly (meth) acrylic acid, polyitaconic acid, a copolymer of (meth) acrylic acid and maleic acid, Data) copolymer of acrylic acid and styrene; and the like. Here, "(meth) acryl ..." means "acryl ..." and Z or "methacryl ...".

 Examples of the acid anhydride that forms an ester bond and an amide bond include aliphatic carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; and aromatic acid anhydrides such as fumaric anhydride. .

Examples of the hydroxyl group-containing compound that forms an ester bond include (A1) and (A2); polyols and polyphenols among the active hydrogen-containing compounds described in the description of the polyol (A); 3 to 24 unsaturated alcohols (r), such as aryl alcohol and propanol, (poly) oxyalkylene ethers of unsaturated alcohols (3 to 24 carbon atoms) (2 to 8 carbon atoms in the alkylene group, polymerization Degree: n = 1 to 30, where the degree of polymerization n indicates the degree of polymerization of the (poly) oxyalkylene segment.) For example, (poly) oxypropylene (n = l to 30) Monoallyl ether and (poly) oxybutylene (n = l to 20) monopropenyl ether; polyvinyl alcohol (degree of saponification 70 to 100, And polyol polymers having a number average molecular weight of 1,000 to 10,000). Examples of the alkylene oxide include those having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide (hereinafter abbreviated as SO), and Combinations of two or more of these (block addition and Z or random addition) may be mentioned.

 Examples of the lactone that forms an ester bond include those having 5 to 12 carbon atoms, such as lactone, enantolactone, laurolactone, and pendenolactone.

 Examples of the active hydrogen-containing compound that generates an amide bond include amines among the active hydrogen-containing compounds described in the description of the polyol (A).

 Examples of the lactam that forms an amide bond include those having 5 to 12 carbon atoms, such as caprolactam, enantholactam, laucolactam and pendecanolactam.

 Examples of the aminocarboxylic acid that forms an amide bond include aminocarboxylic acids having 2 to 18 carbon atoms, such as glycine, alanine, valine, leucine, isoleucine, and phenylalanine; Acids, ω-aminoenanthic acid, ω-aminocaprylic acid, ω_aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

As the acid and diamine used to form the imid bond, known acids and diamine used for synthesizing ordinary polyimide resins can be used. Examples of the acid include 3,4,3 ', 4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid and pyromellitic acid. Aromatic tetracarboxylic acids, these Acid anhydrides and ester compounds of these acids. Examples of the diamine include aromatic diamines having 6 to 18 carbon atoms such as 4,4′-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine and 4,4 ′ diaminodiphenyldimethylamine. No.

 As the isocyanate compound used to form a urethane bond or a urea bond, a known isocyanate compound used for synthesizing an ordinary polyurethane resin can be used. For example, 2,4- or 2,6-tolylene diisocyanate (TD I), crude TDI, 2,4 'one or 4,4'-diphenylmethane diisocyanate (MD I) and crude MD I {Crude diaminodiphenylmethane (condensation product of formaldehyde and aromatic amine, aniline or a mixture thereof; mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of trifunctional or higher polyamine) Phosgenated product; polyallyl polyisocyanate (PAP I)} etc. (excluding carbon in NCO group, the same applies to the following isocyanates) Aromatic polyisocyanate having 6 to 20; Aliphatic polycisyanates having 2 to 18 carbon atoms, such as methylene diisocyanate and lysine diisocyanate; disophoron dicysocyanate and dicyclohexylmethanediene Alicyclic polyisocyanate having 4 to 15 carbon atoms such as cyanate; araliphatic polyisocyanate having 8 to 15 carbon atoms such as xylylene disoocyanate; modification of these polyisocyanates (Eg, urethane group, carbodiimide group, arophanate group, urea group, burette group, uretdione group, uretonimine group, isocyanurate group and modified product containing Z or oxazolidone group); and mixtures of two or more of these. Can be

The active hydrogen-containing compounds used to form urethane or urea bonds are (Al), (A2) and polyols described above. The active hydrogen-containing compound described in the description of (A) can be used. In (bl) used in the production method of the present invention, an ester bond, an amide bond. A urethane bond, a urea bond or an imide bond may be formed by a commonly known esterification reaction, amidation reaction, urethanization reaction, urea bond. It can be obtained by a chemical reaction or an imidization reaction.

 For example, an ester bond or an amide bond can be formed by charging a predetermined amount of a carboxylic acid or an acid anhydride and an active hydrogen-containing compound into a reaction tank and performing a dehydration reaction at 50 to 250 ° C. In addition, the dehydration reaction can be performed under reduced pressure, normal pressure, and increased pressure. It can also be obtained by an addition reaction of a carboxylic acid or an acid anhydride with an alkylene oxide.

 The ratio [equivalent ratio] between the carbonyl group of the carboxylic acid or the acid anhydride and the active hydrogen atom of the active hydrogen-containing compound is usually 0.01 Z1 to 0.98 Z1, preferably 0.1. 1 to 0.8 Z1.

 In the above-mentioned esterification and amidation reaction, a known esterification catalyst can be used. Examples of the catalyst include an antimony catalyst such as antimony trioxide; a tin catalyst such as monobutyl sulphoxide; a titanium catalyst such as tetrabutyl titanate; a zirconium catalyst such as tetrabutyl zirconate; Metal acetate catalysts such as zirconyl and zinc acetate; and combinations of two or more thereof. The amount of the catalyst to be used is generally 0.1 to 5% by mass, based on the total mass of the carboxylic acid and the active hydrogen-containing compound.

 In addition, the amide bond may be prepared by charging a predetermined amount of lactam to the reaction tank in addition to the above, and subjecting it to a ring opening reaction at 50 to 250. It can also be produced by a polycondensation reaction at 0.

The imid bond is formed by N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide. It can be produced by reacting an acid and diamine at 60 to 130 ° C using an organic polar solvent such as side to synthesize an amic acid, followed by dehydration at 60 to 400. A catalyst can be added for the purpose of accelerating the imidization reaction. Specific examples of the catalyst include basic compounds such as triethylamine and 2-methylimidazole. The amount of catalyst is usually from 0.01 to 5% by weight, based on the total weight of acid and diamine.

 A urethane bond or a urea bond is prepared by charging a predetermined amount of an isocyanate compound and an active hydrogen-containing compound into a reaction tank and reacting them at 25 to 150 ° C. The equivalent ratio XI 00 of the sosinate index [(NCO group Z active hydrogen atom-containing group)] is usually 80 to: L40, preferably 85 to: L20, particularly preferably 95 to: L1. 5

 At the time of the urethanization reaction, a catalyst that is usually used for a polyurethane reaction can be used to accelerate the reaction. Examples thereof include amine catalysts such as triethylenediamine and N-ethylmorpholine; tin catalysts such as stannous octoate and dibutyltin dilaurate; and other metal catalysts such as lead octanoate. The amount of the catalyst is usually 0.001 to 5% by mass based on the mass of the isocyanate compound and the active hydrogen compound. Specific examples of the ethylenically unsaturated compound (bl) in the production method of the present invention are shown below.

Examples of the compound having one double bond in the molecule include aliphatic alcohols (1 to 24 carbon atoms) (poly) oxyalkylene (2 to 8 carbon atoms in the alkylene group) and unsaturated unsaturated dicarboxylic acids of ether ( C4 to C24 esters, for example, polyoxypropylene (n = 4 to 30) monomethyl ether maleic diester, polyoxypropylene (n == 3 to 30) monobutyl ether fumaric acid diester and Busu Noorpoli Oxybutylene (n = 2 to 20) · Polyoxyethylene (n = 2 to 10) Itaconic acid diester of random adduct; aliphatic alcohol (1 to 24 carbon atoms) polyoxyalkylene (2 to 20 carbon atoms of alkylene group 8) Ether (meth) acrylate, for example, polyoxypropylene [n = 8 (7) to 30] monomethyl ether (meth) acrylate [However, the numbers in parentheses in n are the values for 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 ( Polyoxyalkylene having 3 to 24 carbon atoms (C 2 to C 8 alkylene group) ether, for example, polyoxypropylene (n = 4 to 30) monooleyl ether, polyoxypropylene (n = 8 to 30) Monoallyl ether; unsaturated aliphatic monocarboxylic acid (3 to 24 carbon atoms) polyoxyalkylene (2 to 8 carbon atoms in alkylene group) ester, for example, oleic acid propylene oxide having a number average molecular weight of 500 or more ( n = 2 to 30) · ethylene oxide (n = 2 to 10) random adduct;

Examples of the compound having two double bonds in the molecule include polyalkylene (the alkylene group has 2 to 8 carbon atoms) glycol di (meth) acrylate, for example, polypropylene dalicol [n = 7 (6) to 30] Di (meth) acrylate and polybutylene glycol [n = 6 (5) -20] di (meth) acrylate; unsaturated alcohol (3-24 carbon atoms) aliphatic carboxylic acid (2-24 carbon atoms) diester, For example, polyoxypropylene (n = 3-30) succinic diester of monoallyl ether, polyoxypropylene (n = 3-30) adipic diester of monoallyl ether, polyoxypropylene (n = 3-30) ) Succinic diester of monopropenyl ether; and the like. Examples of those having three double bonds in the molecule include triesters of unsaturated fatty acids (3 to 24 carbon atoms) of trihydric alcohols having 3 to 12 carbon atoms, for example, glycerin polyoxypropylene [n = 5 (4) to 30] ether tri (meth) acrylate, trimethylolpropanepolyoxypropylene [n = 4 (3) to 30] ether tri (meth) acrylate, penyu erythritol 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; unsaturated alcohol (3 to 24 carbon atoms) aliphatic carboxylic acid (3 to 24 carbon atoms) triester, for example, allylic alcohol (poly) Hexanetricarponic acid triester of xylene (n = l-30) ether; unsaturated alkyl group-containing ether compound, for example, glycerin polyoxypropylene (n = 5-30) ether of triaryl ether; Can be

Examples of the compound having four or more double bonds in the molecule include unsaturated fatty acids (3 to 24 carbon atoms) of polyhydric (4 to 8 or more) alcohols, for example, having a number average molecular weight of 5 Polyglycerin (n = 3 to 4) poly (meth) acrylate with a number average molecular weight of 500 or more Polyglycerin (n = 2 to 4) polyolate with a number average molecular weight of 500 or more Diphenyl erythritol poly with a number average molecular weight of 500 or more (Meth) acrylate, polyglycerin with a number average molecular weight of 500 or more (n = 2 to 4) (poly) oxypropylene (n = l to 30) poly (meth) acrylate, pentaerythritol polyoxypropylene [η = · 3 (2) to 30] ether tetra (meth) acrylate, sorbynone polyoxybutylene (η = 2 to 20) ether tetra (meth) acrylate, polyvinyl alcohol (ken Degree 7 0 to; 0, 0, number average molecular weight 1, 000 to 100, 000) (meth) acrylate; polycarboxylic acid ester of unsaturated alcohol (3 to 24 carbon atoms) (number average molecular weight 1, 0 00 ~: L 0,000), for example, allylic alcohol (poly) oxypropylene (n = l ~ 30) hexanetetracarboxylic acid ester of ether, (meth) acrylic acid polymer and polyester of acryl alcohol (Number-average molecular weight 1,000-: L 0,000), polyester of maleic acid polymer and aryl alcohol (number-average molecular weight 1,000-0,100,000); unsaturated alkyl group Containing ether compounds, for example, tetraglycerin polyallyl ether having a number average molecular weight of 500 or more, polyglycerin having a number average molecular weight of 500 or more (n = 2 to 4) (poly) oxypropylene (n = l to 3) 0) Polyallyl ether of ether; unsaturated Polyester of rubonic acid (C4 to C22) with glycols (number average molecular weight of 50,000 to 10,000), for example, polyester of maleic acid and ethylene daricol (number average molecular weight of 500 to 10 Polyester of maleic acid and diethylene glycol (number average molecular weight 500 to 10,000), Polyester of maleic acid and propylene glycol (number average molecular weight 500 to 100,000), maleic acid And 1,3- or 1,4-butanediol polyester (number-average molecular weight: 500-100, 000); itaconic acid and ethylene glycol polyester (number-average molecular weight: 500-100,000) ), Polycondensates of itaconic acid and diethylene glycol (number-average molecular weight: 50,000 to 10,000), polyesters of maleic acid and polyoxypropylene glycol (n = l to 30) (number-average molecular weight: 500 ~ 1 0, 000), polyester of itaconic acid and polyoxypropylene glycol (n = 1 to 30) (number average molecular weight 500 to 10,000) and fumaric acid and polyoxybutylene glycol (n = 1 to 20). Polyester (number average molecular weight 500-; L 0, 000); And the like.

 Among them, 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 (in the case of two or more, a non-conjugated double bond) or a derivative thereof, for example, acrylic acid, mesyacrylic acid, maleic acid Examples thereof include carboxylic acids having 3 to 24 carbon atoms such as acids, fumaric acid, itaconic acid, citraconic acid and oleic acid; and acid anhydrides such as maleic anhydride, itaconic anhydride and sydraconic 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. Acids; aromatic carboxylic acids having 7 to 18 carbon atoms, such as isophthalic acid and terephthalic acid; alicyclic carboxylic acids having 6 to 20 carbon atoms, such as 1,4-cyclohexanedicarboxylic acid and tetrahydrofluoric acid And the like.

As the glycols (Q), among the active hydrogen-containing compounds described in the description of the polyol (A), polyhydric alcohols and phenols, and the above-mentioned 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 and neopentyldaricol, And E〇, PO, B And alkylene oxides such as 〇 and so, and more preferably, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyldaricol, E〇 and PO. Examples of the aromatic hydrocarbon monomer (b 2 _l) include styrene, α-methylstyrene, hydroxystyrene, and chlorostyrene.

 Examples of the unsaturated nitriles (b2-2) include acrylonitrile and methacrylonitrile.

 (Meth) acrylic esters (b2-3) include methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and pendecyl (meth) acrylate. , Dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, okdecyl (meth) acrylate, eicosyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as docosyl (meth) acrylate (alkyl groups having 1 to 24 carbon atoms); hydroxypolyoxyalkylene mono (meth) acrylates;

Other ethylenically unsaturated compounds (b 2 _ 4) include (meth) 7 acrylamide; (meth) acrylic acid and other vinyl group-containing carboxylic acids and derivatives thereof; and aliphatic hydrocarbons such as ethylene and propylene. Monomers: Fluorine-containing vinyl monomers such as perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate; Nitrogen-containing vinyl monomers such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicon Α-olefins, alkylolefin compounds such as 3-olefins and polyisobutenes; Cyclic olefin compounds such as cyclopentadiene and norbornadiene;

 Among these, (b2-1) and (b2-2) are preferable, and styrene and / or acrylonitrile are more preferable.

 As a production method for obtaining (I), when the method (i) is used, (b 1) is usually at least 5% by mass, preferably at least 10% by mass, based on the total amount of (b) used. Particularly preferably, it is 15 to 99% by mass, most preferably 20 to 80% by mass.

 By setting the amount of (b 1) to 5% by mass or more, it is possible to prevent the viscosity of the obtained polymer polyol from increasing, which is preferable.

 In the production of the polymer polyol composition of the first invention or the second invention, the ethylenically unsaturated compound (b) used in the method (i) other than the method of the fifth invention includes a polymerizable vinyl group. It has at least one, and the usual one used for the production of the polymer polyol composition can be used, and (b2-1), (b2-2), (b2-3), (b 2-4) and mixtures of two or more of these.

 Of these, (b2-1) and (b2-2) are preferred, and styrene and Z or acrylonitrile are more preferred.

 In the ethylenically unsaturated compound used in the method other than the method (i), an aromatic hydrocarbon monomer (b2-1), an unsaturated nitrile (b2_2),

The mass ratio of (meth) acrylates (b2_3) and other ethylenically unsaturated compounds (b2-4) to the total amount of (b) used depends on the required physical properties of polyurethane. Although not particularly limited, an example is as follows.

(b2-1): usually 0 to: L 00 mass%, preferably 20 to 80 mass% (b2-2): usually 0 to 95 mass%, preferably 20 to 80 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. When the polymer polyol (I) is obtained by a method other than the fifth invention, at least a part of (b) ( By using a bifunctional or more (preferably 2 to 8 functional) polyfunctional vinyl group-containing monomer (b2-5) (preferably 0.05 to 1% by mass), the strength of the polymer can be further improved. Can be Examples of the polyfunctional vinyl group-containing monomer include divinyl benzene, ethylene di (meth) acrylate, polyalkylene (having 2 to 8 carbon atoms in the alkylene group) glycol di (meth) acrylate, pentaerythritol triaryl ether, and trimethylolpropanetri (meth). A) Acrylate and the like.

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

 The polymerization of the radical polymerizable compound can be performed in the same manner as in the polymerization of a conventional polymer polyol. For example, a method of polymerizing an ethylenically unsaturated compound (b) in a polyol (A) containing a dispersant (D) in the presence of a polymerization initiator (US Pat. No. 3,338,351) Etc.).

 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 solvent and a chain transfer agent can be used.

As the radical polymerization initiator, those which generate free radicals to initiate polymerization can be used. For example, 2,2, -azobisisobutyronitrile, 2,2, -azobis (2,4-dimethylvaleronitrile) ), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexyl) San 1-Alpunitrile), 2,2'-Azobis (2,4,4-trimethylpentane), Dimethyl 2,2'-Azobis (2-methylpropionate), 2,2'-Azobis [2- Azo compounds such as (hydroxymethyl) propionitrifle] and 1,1'-azobis (1-acetoxy-1-1-phenylethane); dibenzoyl peroxide, dicumyl varoxide, bis (4-tert-butylcyclohexyl) peroxide Organic peroxides such as carbonate, benzoyl peroxide, lauroyl peroxide and persuccinic acid; and inorganic peroxides such as persulfate and perborate. These can be used in combination of two or more.

 The amount of the radical polymerization initiator used is usually from 0.05 to 20% by mass, preferably from 0.1 to 15% by mass, particularly preferably from 0.2 to 10% by mass, based on the amount of (b) used. It is expressed in mass%. 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. It is excellent in that sufficient form compression hardness can be obtained.

 Examples of the solvent include toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, octene, nonene, decene, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, isopropyl alcohol and n —Buynool and the like. The amount of the solvent used is usually 0 to 50% by mass based on the amount of (b) used.

 Examples of the chain transfer agent include alkyl mercaptans such as dodecyl mercaptan and mercaptoethanol; alcohols such as isopropyl alcohol, methanol, 2-butanol and aryl alcohol; carbon tetrachloride, carbon tetrabromide and chloroform. Halogenated hydrocarbons such as mouth form are exemplified.

The amount of chain transfer agent used is usually 0 to 2 based on the amount used in (b). %.

Examples of polymerization initiators in polymerization methods other than radical polymerization include, in coordination dianion polymerization, organic alkyl compounds of various metals of Groups I, II, and III of the periodic table, and metal salts of Groups IV to VII. And an initiator composed of a combination of the above. Further, in the metathesis polymerization, WC 1 ₆ and Mo C 1 ₅ and an organic aluminum two © beam consists of a combination of initiators.

 In order to obtain the polymer polyol composition (I), the polymer particles (B) separated from the polymer polyol composition obtained by polymerizing (b) in the polyol are mixed with the polymer polymer (A) containing no soluble polymer. In the above method (ii) of mechanically dispersing the polymer particles,

 (B) is a vinyl polymer or a polymer particle obtained by a polycondensation or polyaddition reaction, and is usually a particle of 0.1 to 50 m. As the polymer particles (B), a solvent is added, if necessary, from a general polymer polyol obtained by polymerizing an ethylenically unsaturated compound (b) in the presence of a polymerization initiator in a polyol, followed by centrifugation. Use polymer fine particles separated by settling with a separator. Further, polymer fine particles produced by emulsion polymerization / suspension polymerization known as a method for producing polymer particles can also be used.

 As (B), particles obtained by polymerizing (b) in polyol (A) are preferred from the viewpoint of ease of the process.

 (ii) In the method of the [sixth invention], the solvent optionally used includes, for example, hydrocarbon solvents such as toluene, xylene, hexane, heptane, octene, nonene, and decene; methanol, isopropyl alcohol And aprotic polar solvents such as dioxane, acetonitrile, N, N-dimethylformamide and N, N-dimethylacetamide.

The polymer polyol after the polymerization reaction is centrifuged by adding a solvent if necessary. Any device that mechanically re-disperses the released polymer into the polyol (A) can be used as long as it can disperse or crush using the principle of collision, impact, and shear, regardless of its mechanism, structure, or material. .

 As an example of a dispersing machine or a crushing machine used in the present invention, a dispersing machine (homogenizer; manufactured by APV GAUR IN) that presses a liquid and collides with a metal wall (valve) to tear and disperse the liquid. Are listed.

 A fourth invention of the present invention relates to a polymer polyol composition comprising a polyol (A) and polymer particles (B) dispersed in (A), wherein (B) is (A) a dispersion medium comprising (A) The ethylenically unsaturated compound (b) is polymerized in the presence of a dispersant (D ') having a solubility parameter of SP d, the difference between the solubility parameter of SP and SP a of 0.8 or less. The polymer polyol composition is a polymer polyol composition (III), which is a particle obtained by further mechanically dispersing or pulverizing, and the seventh invention is the production method of the above (III).

 In the fourth invention, as the dispersion medium, the above-mentioned polyol (A) may be used alone, or (A) and an organic solvent may be used in combination.

 Examples of the organic solvent to be used include the same organic solvents as those exemplified in the sixth invention.

 The content of the organic solvent in the dispersion medium is arbitrary, but is usually 0 to 80% by mass, and preferably 1 to 50% by mass.

The dispersant (D ') used in the fourth invention includes a solubility parameter SP such that the absolute value of the difference between the solubility parameter of the polyol and SPa is usually 0.8 or less, preferably 0.6 or less. It is necessary to select a dispersant having d. By setting the absolute value of the difference between the solubility parameters to 0.8 or less, the dispersibility and stability of the polymer polyol are improved, and the It is preferable because aggregation and sedimentation can be prevented.

 Here, the solubility parameter is expressed by the square root of the ratio of the density of aggregation to the molecular volume, as shown below.

[Solubility parameter 1] = (ΔΕ / V) ^1/2

 Here, ΔΕ represents the cohesive energy density. V represents the molecular volume, and its value is calculated by Robert F. Fedoors et al., For example, Polymer Engineering and Science, Vol. 14, Pp. 151-154. Taking the solubility parameter for a typical resin as an example, the values of the vinyl polymer are as follows: polystyrene = 10.6, polyacrylonitrile = 14.4, methyl methyl acrylate = 9.9; Polyethylene render = 9.4, polypropylene glycol = 8.7; Polyolefin = 8.6, polypropylene = 8.0; Polyester terephthalate = 12.4 for polyester Polybutylene terephthalate = 11.1; Polyamide values are described as 6-nylon = 11.9 and 6,6-nylon = 11.9. Other resins can 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, there may be a slight deviation from these values due to the difference in the fine structure or the structure of the resin terminal.

 The dispersant (D ') of the present invention may be the same as the dispersant (D) as long as it satisfies the above-mentioned condition of SP value.

Examples of dispersants (D ') include polypropylene glycol and glycidin The compound obtained by reacting with dimethyl acrylate has a solubility parameter SPd of 8.8 for the compound described above, and a difference from SPa when the polyether (A) is propylene glycol. It is 0.1.

 In the fourth invention, the ethylenically unsaturated compound (b) has at least one polymerizable vinyl group, and a known compound used in the production of a polymer polyol can be used. Specifically,

(b2-1), (b2-2), (b2-3), (b2-4), and a mixture of two or more of these.

 Of these, (b2-1) and (b2-2) are preferred, and styrene and Z or acrylonitrile are more preferred.

 The mass ratio of these (b) to the total amount 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.

 (b 2-1): usually 0 to: 100 mass%, preferably 20 to 80 mass% (b 2-2): usually 0 to 95 mass%, preferably 20 to 80 mass% (b 2-3): 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. By using a part (preferably 0.05 to 1% by mass) of the above-mentioned bifunctional or more (preferably 2 to 8) polyfunctional vinyl group-containing monomer-(b2-5), Strength can be further improved.

The polymer polyol of the fourth invention is characterized in that even if the content of the polymer particles in the polymer polyol is high, the viscosity is low, and the content of the polymer particles is usually 30 to 75% by mass, preferably 40 to 75% by mass. 770% by mass, and more preferably 45-60% by mass. When the polymer particle content is 30% by mass or more, sufficient foam compression hardness can be obtained, which is preferable. Also poly When the content of the polymer particles is 75% by mass or less, aggregation and sedimentation of the polymer particles can be prevented, and a polymer polyol having good handleability can be obtained.

 In the fourth invention, the polymerization of the polymer polyol can be carried out in the presence of the dispersant (D ′) in the same manner as the above-mentioned usual polymerization method of the polymer polyol.

 In the fourth invention, as the polymerization initiator used in the polymerization of the polymer polyol, the radical polymerization initiator described above in the first and second inventions can be used.

 The amount of the radical polymerization initiator to be used is usually 0.05 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.1 to 5% by mass, based on the mass of the ethylenically unsaturated compound (b). It is 2 to 2.5% by mass. By controlling the amount of the polymerization initiator to be 0.05 mass% or more, it is possible to prevent a decrease in the polymerization rate of (b) and sufficiently increase the content of the polymer particles composed of (b) in the polymer polyol. it can. When the content is 10% by mass or less, it is possible to prevent a decrease in the molecular weight of the polymer particles, and a polyurethane foam having a sufficient foam compression hardness can be obtained, which is preferable.

 If necessary, chain transfer agents, for example, alkyl mercaptans such as dodecyl mercaptan and mercaptoethanol; alcohols such as isopropyl alcohol, methanol, 2-butanol, and aryl alcohol; The polymerization can be carried out in the presence of a halogenated hydrocarbon such as carbon chloride, carbon tetrabromide, and black form.

In the fourth invention, the polymer polyol (III) can be obtained by physically mechanically dispersing or mechanically pulverizing polymer particles dispersed in the polymer polyol obtained by polymerization. In this case, the polymer—the polymer (B) is not separated once from the polymer polyol without the polymer. The polymer particles (B) are further dispersed mechanically while the polymer particles (B) are contained in one polyol. For example, polymer polyol is sent from the polymerization reactor to a disperser or crusher. (2) There is a method of temporarily storing in a storage tank from the polymerization tank and sending it to a disperser or crusher.

 The mechanism of dispersing and breaking the frame includes those utilizing collision and impact, and those utilizing shear.If the device can disperse or crush by using a device based on those principles, the mechanism is used. Regarding the type of disperser or crusher used in the present invention, a disperser (homogenizer; which tears and disperses the liquid by pressurizing the liquid and colliding with a valve). A.P.V. GAUR IN). The particle size of the polymer particles (B) in the polymer polyol after polymerization is usually 3 m or less, preferably 2 m or less. The polymer polyol containing the polymer particles (B) is dispersed or crushed by a disperser. And forcedly disperse and pulverize to make polymer particles (B) finer to obtain polymer polyol (III). The particle size of the polymer particles after dispersion and crushing is usually 1 m or less, preferably 0.5 m or less. [The particle size is measured with a light scattering particle size distribution analyzer LA-700 (manufactured by Horiba, Ltd.). ]

 The temperature after dispersing and crushing is 0 to 100 ° C., preferably 5:50. Further, when the polymer particles (B) in the polymer polyol are mechanically dispersed or mechanically crushed, they may be diluted with a solvent, if necessary. As the solvent, those exemplified as the solvent that can be used in combination with (A) in the dispersion medium described above can be used. The number of mechanical dispersion or crushing treatments of the polymer-polyol is usually 1 to 20 times, preferably 2 to 10 times. The solvent after the dispersion treatment is removed under reduced pressure.

The removal conditions are normal pressure or reduced pressure (for example, a reduced pressure of 20 to 3 OmmHg) at a temperature of 60 to 100 ° C, and the residual solvent amount is based on the polymer polyol. Preferably it is 5 O pm or less.

 In the fourth invention, the content of the polymer particles in the polymer polyol is usually 30 to 75% by mass, and the viscosity of the polymer polyol obtained by the polymerization reaction is 2, 000 to: L 0 0, OO OmP a's (25), and the viscosity as a result of physically dispersing or mechanically pulverizing after the polymerization reaction is 500 to 20 000 mPas (at 25).

 In the fourth invention, the viscosity of the polymer polyol (III) varies depending on the content of the polymer particles, but is usually from 500 to 20, OO OmPas (at 25), preferably from 700 to 1 5, 0 0 0 m Pa-s (25 ° C). By setting the viscosity of the polymer polyol (III) to 20.000 OmPas (25) or less, it is possible to obtain a polymer polyol having good handleability, and to reduce the viscosity of the polymer polyol (III). A polyurethane foam having a sufficient foam compression hardness can be obtained by setting the pressure to 500 mPa's (25 or more).

 Among the production methods of the fifth, sixth and seventh inventions, the fifth and sixth inventions are preferred, and the production method of the fifth invention is more preferred.

 An eighth invention of the present invention is a method for producing a polyurethane resin, comprising using the polymer polyol composition according to any one of the first invention to the fourth invention as at least a part of a polyol component.

In a method for producing a polyurethane resin by reacting a polyol component and an isocyanate component, if necessary, in the presence of a catalyst, a foaming agent, a foam stabilizer, and other additives, the polymer obtained by the production method of the present invention is used. If necessary, other known active hydrogen atom-containing compounds can be used in combination with the polyol composition. As the other active hydrogen atom-containing compound, other high molecular weight polyols (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 (T), polyether polyols, polyester polyols, modified polyols, and mixtures thereof can be used.

 Examples of the polyether polyol include the same ones as the polyester polyol exemplified in the section of the above-mentioned polyol (A 1).

 Examples of the polyester polyol include the above-mentioned polyhydric alcohols (eg, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). Or a mixture thereof with a trihydric or higher alcohol such as glycerin or trimethylolpropane) and an ester-forming derivative such as the polycarboxylic acid or its anhydride or lower ester (eg, adipic acid, sebacic acid, anhydride) Condensation reaction product with maleic acid, phthalic anhydride, dimethyl terephthalate, etc .; addition reaction product of alkyleon oxide (EO, P〇, etc.); ring-opening of lactone (ε-caprolactone, etc.) Examples include those obtained by polymerization.

 As modified polyols, polydiene polyols (such as polybutadiene polyol), natural polyols such as acrylic polyols and castor oil, and modified polyols thereof can also be used.

 These other polyols usually have 2 to 8, preferably 3 to 8, hydroxyl groups and usually have a hydroxyl equivalent weight of 200 to 400, preferably 400 to 300. are doing.

 Particularly preferred are polyester polyols.

As the low molecular weight active hydrogen atom-containing compound (U), at least two (preferably two to three, particularly preferably two) active hydrogen atoms (hydroxyl, amino, mercapto, etc., preferably hydroxyl) With a molecular weight of 5 0 0 or less (preferably 60 to 400) compounds, for example, low molecular weight polyols and amino alcohols.

 Low-molecular-weight polyols include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyldaricol, and hexanediol; glycerin, trimethylolpropane, Polyhydric alcohols having 3 to 8 or more valents such as pentaerythritol, diglycerin, α-methyldarcoside, sorbitol, xylitol, mannitol, dipentyl erythritol, glucose, fructose, sucrose; Low molecular weight (for example, molecular weight of 200 to 400) polyhydric alcohol alkylene oxide additives (polyethylene glycol, polypropylene glycol, etc.); low molecular weight diols having a ring structure, for example, propylene oxide of bisphenol II Thing, and the like.

 The monoamino or dialkanolamines (monoethanolamine, diethanolamine, monopropanolamine, etc.) are mentioned as the amino alcohol.

 Of these, low molecular weight polyols, particularly diols, are preferred. Specifically, ethylene glycol, 1,4-butanediol, neopentyl alcohol, 1,6-hexanediol, It is a mixture of more than one species.

The polymer polyol group in the entire polyol component (Z) [Polymer polyol composition (I), (II) or (III) and, if necessary, (T) and Z or (U)] in the method for producing the polyurethane of the eighth invention. The amount of the product is preferably at least 5% by mass, more preferably at least 10% by mass, particularly preferably at least 20% by mass. When the amount of the polymer polyol composition is 5% by mass or more, the pressure of the foam when urethane foam is used Easy to set. The content of (B) in the whole polyol component (Z) is preferably 5 to 75% by mass, and more preferably 7 to 55% by mass. The content of (T) is preferably 0 to 95% by mass, more preferably 0 to 80% by mass. When (T) is 95% by mass or less, the foam tends to have a compression hardness.

 Further, the content of (U) is preferably 0 to 30% by mass, and more preferably 0 to 10% by mass. When the amount of (U) is 30% by mass or less, the exothermic temperature during the reaction does not become too high, and there is no possibility of scorch.

As the organic polyisocyanate used for producing the polyurethane resin, known organic polyisocyanates conventionally used for producing a polyurethane resin can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbons in the NCO group) (eg, 2,4- and / or 2,6-tolylenediisocyanate). Cyanate (TDI), crude TDI, 2,4'- and Z or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminodiphenylmethane {formaldehyde and aromatic amines Condensation product with aniline) or a mixture thereof: Phosgenated compound of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a triamine or higher functional polyamine}: polyallylpolyisocyanate (PAP I) etc.]; an aliphatic polyisocyanate having 2 to 18 carbon atoms (for example, hexamethylene diisocyanate, lysine diisocyanate, etc.); an alicyclic having 4 to 15 carbon atoms Poly Sociate ( For example, isophorone diisocyanate, dicyclohexylmethane diisocyanate); an araliphatic polyisocyanate having 8 to 15 carbon atoms (for example, xylylene diisocyanate); and modified products of these polyisocyanates (Urethane group, carbodiimide group, aromatic group, urea group, burette group, uretdione group, ureton A modified product containing an imine group, an isocyanurate group or an oxazolidone group); and a mixture of two or more of these.

 Preferred among these are 2,4_ and 2,6-TDI, a mixture of these isomers, crude TDI; 4,4,1 and 2,4, -MDI, these isomers And modified polyisocyanates containing urethane groups, carbodiimide groups, arophanate groups, urea groups, burette groups, and isocyanurate groups, which are derived from a mixture of the compounds, PAP I; and these polyisocyanates.

 The isocyanate index [equivalent ratio X (100) of the (NCOZ active hydrogen atom-containing group)] in the production of the polyurethane resin is usually 80 to 140, preferably 85 to 120, and particularly preferably 95 to 115. It is. It is also possible to introduce a polyisocyanurate group into the polyurethane by setting the isocyanate index significantly higher than the above range (for example, from 300 to 100,000).

 In the production of the polyurethane resin, a catalyst generally used for a polyurethane reaction may be used to promote the reaction. For example, amine catalysts (tertiary amines such as triethylenediamine and N-ethylmorpholine), tin catalysts (stannous octoate, dibutyltin dilaurate, etc.), and other metal catalysts (lead octoate, etc.) ). Of these, amine catalysts and / or tin catalysts are preferred. The amount of catalyst is preferably between 0.001 and 5% by weight, based on the weight of the reaction mixture. In the method of the eighth invention, the reaction is carried out in the presence of a blowing agent if necessary. As the foaming agent, at least one selected from hydrogen atom-containing halogenated hydrocarbons, water, low-boiling hydrocarbons, and liquefied carbon dioxide is used. Specific examples of the hydrogen atom-containing halogenated hydrocarbon,

HC FC (Hide mouth Black mouth Fluorocabon) type (for example, HC FC—123, HC FC—141 b, HC FC—22 and HC FC—142b)

 HF C (Hide mouth fluorocarbon) type (for example, HF C-134a, HF C-152 a, HF C-356m ff, HF C-236 ea, HF C_ 245 ca, HF C_ 245 fa and HF C—36 5 mcf)

And the like.

 Of these, preferred are HCFC-141b, HFC-134a, HFC-356mff, HFC_236ea, HFC-245c a. HFC-245fa, HFC- 365 mcf and a combination of two or more of these.

 The low-boiling hydrocarbon is a hydrocarbon having a boiling point of usually 15 to 70, 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 used is usually not more than 50 parts by mass, preferably 5 to 45 parts by mass, per 100 parts by mass of the whole polyol component (Z).

 When a 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 generally 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 used is usually 4 parts per 100 parts by mass.

The amount of water does not exceed 5 parts by mass, preferably 5 to 40 parts by mass. The amount of water used does not usually exceed 10 parts by mass, preferably 0.5 to 8 parts by mass per 100 parts by mass of (Z). Department. When low-boiling hydrocarbons and water are used together, the amount of low-boiling hydrocarbons used is

The amount is usually not more than 40 parts by mass, preferably 2 to 35 parts by mass per 100 parts by mass of (Z), and the amount of water used is usually 10 parts by mass per 100 parts by mass of (Z). And preferably 0.5 to 8 parts by mass.

 When using liquefied carbon dioxide and water together, the amount of liquefied carbon dioxide

(Z) An amount not exceeding 25 parts by mass per 100 parts by mass, preferably from 0:! To 20 parts by mass, and the amount of water used is usually 1 part per 100 parts by mass of (Z). The amount does not exceed 0 parts by mass, preferably 0.5 to 8 parts by mass. When water alone is used as the foaming agent, the amount of water used is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass per 100 parts by mass of (Z).

 In the method of the eighth invention, if necessary, the reaction may be carried out in the presence of a foam stabilizer and other additives as described below. For example, foam stabilizers (dimethylsiloxane-based, polyether-modified dimethylsiloxane-based, etc.), colorants (dye, pigment, carbon black, etc.), plasticizers (phthalate, adipate, etc.), organic fillers (synthetic short Fibers, hollow microspheres made of thermoplastic or thermosetting resin, etc., flame retardants (phosphate esters, halogenated phosphate esters, melamines, phosphazene derivatives, etc.), antioxidants (triazoles, The reaction can be carried out in the presence of known auxiliary components such as benzophenones, antioxidants (hindered phenols, hindered amines, etc.), internal mold release agents and bactericides.

With respect to the use amount of these additives with respect to 100 parts by mass of the whole polyol component (Z), the foam stabilizer is preferably 10 parts by mass or less, more preferably 0.5 to 5 parts by mass. The colorant is preferably at most 1 part by mass. The plasticizer is preferably 10 parts by mass or less, more preferably 5 parts by mass. It is as follows. 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 flame retardant is preferably 20 parts by mass or less, and 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 polyurethane resin can be produced by an ordinary 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, an apparatus such as a kneader or an extruder can be used. For example, various types of non-foamed or foamed polyurethane resin can be manufactured in a closed mold or an open mold. 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), a 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 process of the present invention is particularly useful for the production of flexible mold forms and slab foams. It can also be applied to molding by the RIM (reaction injection molding) method. Example

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,% by mass, and mass ratio, respectively. It is as follows. 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 flame retardant is preferably 20 parts by mass or less, and 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 polyurethane resin can be produced by an ordinary method, and can be produced by a known method such as a one-shot method, a semi-prepolymer method, or a pre-polymer method.

 For the production of the polyurethane resin, a commonly used production apparatus can be used. When no solvent is used, for example, a device such as a lower extruder can be used. For example, various types of non-foamed or foamed polyurethane resin can be manufactured in a closed mold or an open mold. 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), a 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 process of the present invention is particularly useful for the production of flexible mold forms and slab foams. It can also be applied to molding by the RIM (reaction injection molding) method. Example

 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,% by mass, and mass ratio, respectively.

4 1 The compositions, symbols, etc. of the raw materials used in Examples and Comparative Examples are as follows,

(1) Polyol (A)

 G 50: a polyol having a number average molecular weight of 3,000 and a hydroxyl value of 55, obtained by adding 50 moles of PO to glycerin on average, 50 OmPa · s (25 t :).

 (2) Carboxylic acid containing reactive unsaturated group (p)

 MA: maleic anhydride

 I A: Conic anhydride

 (3) Saturated carboxylic acid

 A A: Adipic acid

 F A: phthalic acid

 (4) Glycols (Q)

 E G: Ethylene dali call

 DEG: Diethylene glycol

 PP—200: Polyoxypropylene dalicol (number average molecular weight 2

 00)

 P P—400: Polyoxypropylene Dalicol (number average molecular weight 4

 00)

 P〇: Propylene oxide

(5) Other ethylenically unsaturated compounds (b 2)

 ACN: Acrylonitrile

 S t: Styrene

(6) Dispersant (D)

 GMAP: Glycidyl methacrylate adduct of polypropylene glycol (number average molecular weight 3 000)

 SAN: acrylonitrile styrene = 80/20% by mass copolymerization

42 Body (number average molecular weight 5, 000)

 (7) polymerization initiator

 A VN: 2,2,1-azobis (2,4-dimethylvaleronitrile)

 (8) Organic polyisocyanate

 TD I-80: "Millionate T80" [Nippon Polyurethane Industry

 Manufactured by

 (9) Catalyst

 Catalyst A "Neostan U-28 (stannous octoate) [Nitto Kasei Co., Ltd.]

 Catalyst B DAB CO (triethylenediamine) [Nippon Emulsifier

 Manufactured by

 Catalyst C DABC03 3 LV (33% by mass of DABCO in dipropylene blend solution) [Sankyo Air Products Co., Ltd.]

T B T: Tetrabutyltyl titanate

 (10) Foam stabilizer

 "F-242T": Polyether siloxane polymer [Shin-Etsu Silicon Co., Ltd.]

 The number average molecular weight, degree of unsaturation, viscosity, polyol-soluble polymer, and dispersion stability were measured as follows.

<Number average molecular weight>

 Model: HLC— 8 1 2 0 GPC (Liquid Chromatography 1 manufactured by Tosoh Corporation)

 Column: TSK gel Super H4000

 + TSK g e l S up e r H 3 000

 + T S K g e l S Up e r H 2 000

43 (All manufactured by Tosoh Corporation)

 At column temperature 40

 Detector R I (R e r a c t i v e I n d e x Solvent Tetrahydrofuran

 Flow velocity 0.6 ml

 Material concentration 0.25 mass%

 Injection volume 1 0 1

 Polystyrene

 (Manufactured by Tosoichi Co., Ltd .; T SKS TANDARD POLYS TYRENE)

Unsaturation>

 Measured according to the measurement method specified in JISK 557 <

 <Viscosity>

 B L-type viscometer (TOK I MEC)

 Measurement temperature 2 5

 Rotor No No 3 or No 4

 Number of rotations The number of rotations is determined based on the measured viscosity and the number of rotations described above in the description of 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: J A I GE L— 1 H

 + J A I GEL- 2H

 + J A I GEL-3H

 (All manufactured by Nippon Kagaku Kogyo Co., Ltd.)

44 Column temperature 4 o

 Detector R I

 Solvent chloroform

 Flow rate 2.5m l Z min

 Material concentration 0.25 mass%

 Injection volume 4 m 1 X 1 2 times

Dispersion stability>

 ① Leave the polymer polyol in a 140m1 glass sealed container in a 50 ° C constant temperature bath for 30 days.

 (2) After standing, the dispersion stability was visually checked.

 Evaluation criteria

 均一 There was no sediment and it was in a uniformly dispersed state.

 △ There was a sediment, and after the sample bottle was turned 5 times, it was uniformly redispersed.

 X There was a precipitate, and the sample bottle was not redispersed after turning over 5 times. Production Example 1> Production of radically polymerizable compound 1

 In a 1 liter 4-neck flask equipped with a Dimroth condenser and a Dean-Stark trap, put 98 parts of MA and 440 parts of PP-400 into a 4-neck flask. The temperature was raised to 80 with stirring under the reaction (until the end of the reaction) and kept for 1 hour. Next, the temperature was raised to 170, and the reaction was carried out at the same temperature for 6 hours. Then, 0.02 parts of TBT was added and reacted at 170 at room temperature for 2 hours.Unsaturated polyether having a number average molecular weight of 5400, a hydroxyl value of 21 mgKOH / g and an unsaturation degree of 1.86 (X = 538) was obtained. I got a stet (b l①). Where X is the number of double bonds defined above.

45 Is the molecular weight of

 <Production Example 2> Production of radically polymerizable compound 1

 Using the same apparatus and method as in Production Example 1, using MA: 294 parts, PEG-200: 800 parts, a number average molecular weight of 10094, a hydroxyl value of 103 mgK OH / g, and a degree of unsaturation of 2 .74 (Χ = 365) unsaturated polyester (b1 ©) was obtained.

Production example 3> Production of radically polymerizable compound 1

 Using the same apparatus and method as in Production Example 1, using MA: 98 parts, PP—200: 240 parts, a number average molecular weight of 3400, a hydroxyl value of 33 mg KOH g, and an unsaturated degree of 2.96 (X = The unsaturated polyester (b1③) of 338) was obtained.

 <Production Example 4> Production of radical polymerizable compound 1

 Using the same apparatus and method as in Production Example 1, using IA: 118 parts, PP-400: 440 parts, number average molecular weight 5600, hydroxyl value 20 mg KO HZg, degree of unsaturation 1.79 ( An unsaturated polyester (b 1 ④) of X = 555) was obtained.

 <Production Example 5> Production of radical polymerizable compound 1

 MA: 98 parts, PP-400: 400 parts, FA: 296 parts, N-ethylmorpholine 0.1 parts were put into a 1.5 liter pressure reactor. The temperature was raised to 12 O: with stirring under a nitrogen atmosphere (until the end of the reaction) and kept for 2 hours. Next, 2 parts of P〇232 were blown in at 120 ° C. and a pressure of 0.3 mPas over 6 hours. Thereafter, the reaction was further performed at 120 ° C. for 2 hours. An unsaturated polyester (b1⑤) having a number average molecular weight of 110, a hydroxyl value of 102 mgK OH / g, and an unsaturation degree of 0.98 (X = 1102) was obtained.

 <Production Example 6> Production of radical polymerizable compound 1

46 Using the same apparatus and method as in Production Example 1, using MA: 280 parts and DEG: 370 parts, the number average molecular weight was 100, the hydroxyl value was 112 mgK〇H / g, and the degree of unsaturation was 4 An unsaturated polyester (bl 2) of 34 (X = 230) was obtained.

<Production Example 7> Production of radical polymerizable compound 1 7

Using the same apparatus and method as in Production Example 1, using MA: 390 parts and EG: 284 parts, the number average molecular weight was 920, the hydroxyl value was 122 mg KOHZg, and the degree of unsaturation was 5.49 (X = 1 8 2) _c <example 1> was obtained unsaturated polyester (b 1⑦) manufacturing one first polymer polyol

 Into a 1-liter four-necked flask equipped with a Dimroth condenser, 10 parts of SAN and 440 parts of G50 are charged, and after replacement with nitrogen, the mixture is stirred under a nitrogen atmosphere (until polymerization is completed). To 250 parts of unsaturated polyester (bl①), AN: 150 parts, and St: 100 parts, and G50: 50 parts and A in advance. VN: 1 part of the mixed raw material was simultaneously dripped continuously over 1 hour using a dripping pump, and polymerized at 130 for 2 hours. Polymer particle content 50%, hydroxyl value 28 mg KOHZg Thus, a polymer polyol (F-1) having a viscosity of 4500 mPa · s (251 :) was obtained.

<Example 2> Production of polymer polyol 1 2

 In a 1-liter four-necked flask equipped with a Dimroth condenser, add 10 parts of SAN and 90 parts of G50, and after purging with nitrogen, stir under a nitrogen atmosphere (until the end of polymerization). The temperature was raised to 0 ° C., and then a raw material in which unsaturated polyester (b 1 （): 200 parts, AN: 150 parts, and St: 200 parts were mixed in advance, and G 50: 50 parts and AVN: One part of the mixed raw material is simultaneously dripped continuously over 1 hour using a dropping pump at the same time, and polymerized at 130 ° C for 2 hours, polymer particle content 55%, water

47 A polymer polyol (F-2) having an acid value of 25 mgK〇HZg and a viscosity of 4800 mPa-s (25 ° C.) was obtained.

 <Example 3> Production of polymer polyol-1

 Into a 1-liter 4-neck flask equipped with a Dimroth condenser, add 10 parts of SAN and 50 parts of 490 G, and after purging with nitrogen, stir under a nitrogen atmosphere (until polymerization is completed). The raw material was previously mixed with 50 parts of unsaturated polyester (b1③), 200 parts of AN, and 200 parts of St, and 50 parts of G50: AVN: One part of the mixed raw material was simultaneously dropped continuously over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The polymer particle content was 45% and the hydroxyl value was 3 A polymer-polyol (F-3) with 1 mgKOH / g and a viscosity of 400 mPas (at 25) was obtained.

Example 4> Production of polymer polyol— 4

 In a 1-liter four-necked flask equipped with a Jim port cooling tube, add 10 parts of SAN and 340 parts of G50, and after stirring with nitrogen, stir under a nitrogen atmosphere (until polymerization is completed). The temperature was raised to 130 ° C., and then a raw material in which unsaturated polyester (bl④): 400 parts, AN: 100 parts, St: 100 parts was previously mixed, and G 50: A raw material obtained by mixing 50 parts and 1 part of AVN was simultaneously and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 at 2 hours to obtain a polymer particle content of 60% and hydroxyl. A polymer polyol (F-4) having a base value of 22 mgKOH / g and a viscosity of 620 OmPas (at 25) was obtained.

<Example 5> Production of polymer polyol 1

 Into a 1-liter 4-neck flask equipped with a gym-mouth cooling tube, add 10 parts of SAN and 440 parts of G50, and after purging with nitrogen, stir under a nitrogen atmosphere (until the end of polymerization). Temperature rise to 30 and then unsaturated

48 A raw material in which 250 parts of polyester (bl④), AN: 150 parts, and St: 100 parts were mixed in advance, and a raw material in which G50: 50 parts and AVN: 1 part were previously mixed, Each was simultaneously dropped continuously for 1 hour using a dropping pump, and polymerized at 130 at 2 hours, polymer particle content 50%, hydroxyl value 28 mgK〇HZg, viscosity 4700 mPa A polymer polyol (F-5) of -s (at 25) was obtained.

<Example 6> Production of polymer polyol-1

 In a 1-liter four-necked flask equipped with a Dimroth condenser, add 10 parts of SAN and 440 parts of G50. After purging with nitrogen, 130 ° while stirring under a nitrogen atmosphere (until the end of polymerization). C. Then, a raw material in which unsaturated polyester (bl⑤): 250 parts, AN: 150 parts, St: 100 parts was previously mixed, and G50: 50 parts and A VN: One part of the mixed raw material was continuously dropped simultaneously over 1 hour using a dropping pump, and polymerized at 1301: 2 for 2 hours. Polymer particle content 50%, hydroxyl value A polymer polyol (F-6) having 28 mgK〇HZg and a viscosity of 490 OmPas (25) was obtained.

<Example 7> Production of polymer polyol-1

 500 parts of unsaturated polyester (b1®) was placed in a 1-liter four-necked flask equipped with a Jim mouth cooling tube, and after replacement with nitrogen, the mixture was stirred under a nitrogen atmosphere (until polymerization was completed). The temperature was raised to 0 ° C., and then a raw material in which 50 parts of SAN and 400 parts of G50 were mixed in advance was added, and the mixture was stirred at 130 for 3 hours. Thereafter, a raw material obtained by mixing 50 parts of G50 and 1 part of AVN in advance is dropped continuously continuously over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours to obtain polymer particles. A polymer polyol (F-7) having a content of 50%, a hydroxyl value of 28 mg KOHZg and a viscosity of 550 OmPa · s (25) was obtained.

49 Example 8> Production of polymer polyol 1

 Using the same apparatus and method as in Example 7, using (bl⑦) instead of the unsaturated polyester (bl⑥), polymer particle content 50%, hydroxyl value 28 mg KOH / g, viscosity 5640 mPa- s (at 25) of polymer polyol (F-8) was obtained.

 <Example 9> Production of polymer polyol-9

 Put 50 parts of G50 into a 2 L four-necked flask equipped with a temperature controller, vacuum stirring blade, dropping pump, decompression device, Dimroth condenser, nitrogen inlet and outlet, and add 1 part under stirring. The mixture was heated to 25 ° C, and the raw material obtained by previously mixing St 450 parts, ACN 300 parts, GMAP 20 parts, G50: 680 parts, and AVN 4 parts was dropped by a dripping pump for 4 hours. The mixture was dropped continuously to polymerize. Further, unreacted monomers were stripped under reduced pressure. A comparative polymer polyol (F-9) having a polymer particle content of 50%, a hydroxyl value of 28, and a viscosity of 20,000 mPa-s (at 25) was obtained.

Add 800 parts of methanol to 800 parts of (F-9), centrifuge 3 times at 800 rpm for 60 minutes, wash the separated polymer with methanol, and dry under reduced pressure at 30-40. Thus, 350 parts of a polymer was obtained. The polymer was further ground in a mortar, and 350 parts of G 50 and 1400 parts of methanol were added to obtain a dispersion. In addition, this dispersion liquid is homogenized by an APV GAUR IN homogenizer (model No. 15M-8TA), which has a homo-valve inside the device and can change the degree of pressurization of the liquid with a plunger pump. The dispersion treatment was repeated twice. Processing conditions of the dispersion, the dispersion pressure 700 Kg f Zc m ^2, processing speed 60 kg / hr, was performed at the processing temperature 2 5.

 After the dispersion treatment, the viscosity of the polymer polyol (F-10) produced by the method of the present invention obtained by stripping methanol under reduced pressure was 500 OmPa · s (at 25).

50 Example 10> Production of polymer polyol 10

The polymer polyol (F-9) obtained in Example 9 was manufactured by APV G AUR IN, which has a home valve inside the apparatus and can change the degree of pressurization of the liquid with a plunger pump. Dispersion treatment was repeated twice using a homogenizer (model No. 15M-8TA). The processing conditions for the dispersion were a dispersion pressure of 700 kgf Zcm ² , a processing speed of 60 kgZhr, a processing time of 2 minutes, and a processing temperature of 25. After dispersion treatment, the obtained polymer polyol

The viscosity of (F-11) was 9760 mPa-s (at 25).

<Comparative Example 1> Comparative Production Example 1 of polymer polyol 1

 Comparative polymer polyol (F-9) without mechanical dispersion treatment obtained in Example 9

 <Comparative Example 2> Comparative Production Example 1 of polymer polyol 1

 G50: 150 parts, St: 280 parts, AN: 120 parts, GMAP: 8 parts, G50: G50: 150 parts by the same apparatus and method as used in the production of (F-9) in Example 9. 442 parts and A VN: 1.6 parts, polymer particle content 40%, hydroxyl value 33 mgK〇HZg, viscosity 5 540 mPa · s

A comparative polymer polyol (F-12) of (in 25) was obtained.

<Comparative Example 3> Comparative production example 1 of polymer polyol 3

 G50: 175 parts, St: 210 parts, AN: 90 parts, GMAP: 6 parts, G50: G50: 175 parts by the same apparatus and method as used for the production of (F-9) in Example 9. Using 519 parts and AVN: 1.2 parts, a comparative polymer polyol (F-13) having a polymer particle content of 30%, a hydroxyl value of 39 mgKOHZg and a viscosity of 2000 mPa's (at 25) was obtained. .

Examples (1) to (11) and Comparative Examples 1 to 3> Production of Polyurethane Foam

 The polymer polymers of the present invention obtained from Examples 1 to 10 and Comparative Examples 1 to 3

51 Using riols (F-1 to F-8, F_10, 11) and comparative polymer polyols (F-9, F-12, 13), the polyester resin described in Tables 1 and 2 is used. A polyurethane foam was produced according to the foaming formulation shown below at the mixing ratio of the foam. Tables 1 and 2 show the evaluation results of these foam properties. Foaming formula>

 (1) Adjust the temperature of the polymer polyol and the organic polysocyanate to 25 ° C and 2 ° C, respectively.

 (2) Put the polymer polyol, foam stabilizer, water and catalyst in the order of 1 liter in a stainless steel beaker, stir and mix at room temperature (25 ± 2 ° C). Immediately add the organic polyisocyanate and stirrer. (Homodispers: manufactured by Tokushu Kika Co., Ltd., stirring conditions: 2000 rpm x 6 seconds), and the mixture was stirred to foam.

 (3) After the stirring was stopped, the contents were put into a wooden box of 25 x 25 x 10 cm to obtain a polyurethane foam.

52

53 Example Example Comparative Example

 (9) (1 0) (1 1) (1) (2) (3) Polymer voritol F—10 F—1 1 F-6 F-9 F—12 F—1 3 Polymer particle concentration [% by mass ] 50 50 50 50 40 30 Hydroxyl value [mgKOH / g] 28 28 28 28 33 39 Viscosity (25 * 0 [mPas] 5000 9760 4900 20000 5540 2000 Upper limit of viscosity in formula (1) 7800 7800 7800 7800 3200 1580 (at 25) [mP a · s]

 0 6 2 10 8 6 Soluble polymer [% by mass]

Dispersion stability 〇 〇 〇 Δ Δ Δ Polyurethane foam

 Mix ratio [parts]>

Polymer polyol 100 100 100 100 100 100 Water 2.7 2.7 2.7 2.7 2.7 2.7 Catalyst A 0.04 0.04 0.20 0.04 0.04 0.04 Catalyst B 0.30 0.30 0 0.30 0.30 0.30 Catalyst C 0 0 0.30 0 0 0

F-242 T 1.0 1.0 1.0 1.0 1.0 1.0

TD I -80 32.0 32.0 32.0 32.0 33.0 33.9

<Form properties>

Density [kg / m ³ ] 33.7 33.8 32.4 33.4 33.2 33.8

25% I LD 45.7 41.7 44.5 40.3 35.7 32.4 [kgf / 3 14 cm ² ]

Tensile strength [kgf / cm ² ] 1.52 1.48 1.52 1.46 1.57 1.66 Tear strength [kg fZcm] 0.89 0.83 0.86 0.75 0.76 0.71 Elongation at break [%] 70 70 74 65 90 105 Rebound resilience [%] 30 30 32 24 27 28 Breathability [ft ³ / min] 3.9 2.9 2.2 1.3 3.0 3.7 Compression set [%] 28.4 31.4 27.5 37.5 28.2 10.5

54 The evaluation methods of foam properties in Tables 1 and 2 are as follows. Density (kgZm ³ ): Based on JISK 6400—199 7 [Item 5]

2 5% ILD (kgf / 3 1 4 cm ² )

 : JISK 6 382—1 9 9 5 [Item 5.

 3]

Tensile strength (kgf / cm ² ): JIS K630 1—1 9 9 5 [Item

 3]

Tear strength (kgf / cm): JISK6 30 1-1 9 9 5 [Item

 Compliant with 93

Cutting elongation (%): JISK6 3 0 1—1 9 9 5 [Item

 3]

Rebound resilience (%): JIS K6400-1997 [Item

 7]

Breathable (ft ³ Z min): Dow formula Furome Isseki of the Act [AMS COR Inc.]

 (Specimen 5 cmX 5 cmX 2.5 cm) Compression set (%): Based on JISK 6382-19995 [Item 5.5]

Normally, as the physical properties of the urethane foam, density, 1 5-5 0 range of k gZm ³ are preferred, 2 5% I LD, tensile strength, tear strength, elongation at break, modulus of resilience and breathability, The larger the value, the better. The smaller the numerical value of the compression set, the better.

 As is clear from Table 1, the polymer polyols (F-1 to F_8, F-10, 11) of Examples 1 to 10 were compared with the polymer polyol (F-9) of Comparative Example 1. And low viscosity, polyurethane foam

55 Excellent foam properties, especially 25% ILD (hardness), breathability and compression set. The tear strength, tensile strength, elongation at break, and rebound resilience were equivalent or higher. The polymer polyols (F-12, F-13) of Comparative Examples 2 and 3 were the same as the polymer polyols (F-1 to F-8, F-- The viscosity is low because it is less than the polymer (F-9) of Comparative Examples 10 and 11) and Comparative Example 1, but the physical properties of polyurethane foam, especially 25% ILD (hardness) ) Is significantly inferior. In general, the higher the concentration of polymer particles, the lower the tensile strength, elongation at break, rebound resilience, and air permeability, and the higher the compression set, but polyurethane foam using the polymer polyol of the present invention [ Examples (1), (5) to (10)] show the same or higher foam physical properties than Comparative Example 1 having the same polymer particle concentration. Industrial applicability

 ADVANTAGE OF THE INVENTION According to the polymer polyol 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, the polymer polyol with low viscosity and very favorable dispersion stability can be obtained. Therefore, in the production of polyurethane resin and the like, the working efficiency can be significantly improved.

 Furthermore, when a polyurethane resin produced by using the polymer polyol of the present invention as an essential component of the polyol is compared with a polymer polyol having the same viscosity, the case where the polymer polyol of the present invention is used is more conventional. 25% ILD (hardness) and compression set are significantly better than those used. Also, compared to the case where a conventional polymer polyol having the same polymer particle concentration is used, the polymer polyol of the present invention is used.

56 In the case of using the resin, the 25% ILD, air permeability and compression set of the urethane resin can be significantly improved.

 Due to the above effects, the polyurethane resin produced using the polymer polyol of the present invention is extremely suitable as a polyurethane foam for applications such as interior parts of automobiles and interior furnishings of furniture.

57

Claims

The scope of the claims

1. A polymer polyol comprising a polyol (A) and polymer particles (B) dispersed in (A), wherein (B) is formed by polymerizing an ethylenically unsaturated compound (b) in a polyol. In the composition (I), the content of (B) is 35 to 75% by mass based on the mass of (I), and the content of the soluble polymer (P) dissolved in (A) is A polymer polyol composition having an amount of 5% by mass or less based on the mass of (A).

 2. 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 ethylenic in the polyol. In the polymer polyol composition (I) formed by polymerizing the unsaturated compound (b), the content of (B) is 35 to 75% by mass based on the mass of (I); A polymer polyol composition having a Brookfield viscometer (25) of I) having a viscosity V (mPa-s) in the range of the following formula (1).

 V≤ (V a -V a X C / 10) "[e ~ x] (1)

 Where x = 0.0010354X B p 1.5

 V a: viscosity (mP a · s) of Brookfield viscometer at 25 in (A).

 C: Content of (C) in (I) (% by mass)

 B p: Content of (B) in (I) (% by mass)

 : Indicates a power.

 e: base of natural logarithm.

 3. The polymer-polyol composition according to claim 1, wherein the content of (B) in (I) is 45 to 75% by mass.

 4. In (A), in the presence of dispersant (D) and / or diluent (C).

58 3. The polymer according to claim 1, wherein (b) contains 5% by mass or more of an ethylenically unsaturated compound (b 1) having a number average molecular weight of 500 or more in the absence or presence thereof. 4. A polyol composition.

 5. Polyol (A) and polymer particles (B) dispersed in (A), where (B) is an ethylenically unsaturated compound in the polyol

In the polymer polyol composition (II) formed by polymerizing (b), in (A), in the presence of a dispersant (D), in the presence or absence of a diluent (C), a number average Ethylenically unsaturated compound having a molecular weight of 500 or more

A polymer polyol composition obtained by polymerizing (b), containing (b 1) in an amount of 5% by mass or more.

 6. The polymer polyol composition according to claim 4, wherein the molecular weight (X) per double bond of (b 1) is 12,000 or less.

 7. The polymer according to claim 4, wherein (b 1) is an ester of an unsaturated carboxylic acid (p) and a glycol (Q), and an ester of a no or unsaturated alcohol (r) and a carboxylic acid (s). A polyol composition.

 8. The polymer polyol composition according to claim 7, wherein the unsaturated carboxylic acid (p) is one or more carboxylic acids selected from maleic acid, fumaric acid and itaconic acid.

 9. The polymer particles (B) separated from the polymer polyol composition obtained by polymerizing (b) in a polyol contain more than 5% by mass of a soluble polymer based on the mass of (A). 3. The polymer polyol composition according to claim 1, wherein the polymer polyol is mechanically dispersed in (A).

 10. In the polymer-polyol composition comprising the polyol (A) and the polymer particles (B) dispersed in the (A), (B) is the solubility of (A) in the dispersion medium comprising (A). The difference from the parameter one night SP a is 0.8

59 The polymer particles obtained by polymerizing the ethylenically unsaturated compound (b) in the presence of a dispersant (D ′) having the following solubility parameter SP d are further polymerized by mechanically dispersing or pulverizing the polymer particles. A polymer polyol composition (111).

 1 1. A method for producing 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 Z or a diluent (C). The polymer polyol composition (I) or (I) according to any one of claims 1, 2 or 5, using (b) containing at least 5 mass% of an ethylenically unsaturated compound (bl) having a number average molecular weight of 500 or more. Ii) a method for producing a polymer-polyol composition.

 1 2. In a method for producing a polymer polyol composition comprising a polyol (A) and polymer particles (B) dispersed in (A), the method comprises polymerizing an ethylenically unsaturated compound (b) in the polyol. Polymer particles (B) separated from the resulting polymer polyol composition are mechanically dispersed in (A) which does not contain more than 5% by weight, based on the weight of (A), of a soluble polymer. Item 3. A method for producing the polymer-polyol composition (I) according to any one of Items 1 and 2.

 1 3. In a dispersing medium consisting of polyol (A), a dispersant (D ') having a solubility parameter of SPd with a difference of 0.8 or less from solubility parameter SPa of (A) 10. The polymer polyol composition according to claim 10, further comprising mechanically dispersing or pulverizing the polymer particles in the polymer polyol obtained by polymerizing the ethylenically unsaturated compound (b) in the presence of). Production method of product (III).

 14. React the polyol component and the polyisocyanate component in the presence or absence of a foaming agent to produce a foamed or non-foamed polyurethane resin.

60 A method for producing a polyurethane resin, comprising using the polymer polyol composition according to any one of claims 1, 25 and 10 as at least a part of a polyol component.

6 1