WO2011152036A1

WO2011152036A1 - Polymer polyol and method for producing polyurethane

Info

Publication number: WO2011152036A1
Application number: PCT/JP2011/003041
Authority: WO
Inventors: 智寿平野; 興滋加峰; 佐々木　慶
Original assignee: 三洋化成工業株式会社
Priority date: 2010-05-31
Filing date: 2011-05-31
Publication date: 2011-12-08
Also published as: JPWO2011152036A1

Abstract

Provided are a polymer polyol from which polyurethane having a high tensile strength can be produced, and a method for producing polyurethane using a polyol component which comprises said polymer polyol. A polymer polyol (I) comprising polymer microparticles (JR) contained in a polyol (PL), said (JR) comprising an ethylenically unsaturated compound (E) as a constituting unit, wherein (PL) contains a strength-improving agent (b) as will be described hereinbelow and the volume-average particle diameter (R) of (JR) is 0.1-1.5 μm. Strength-improving agent (b): at least one kind of a compound which is selected from the group consisting of an ester compound, a thioester compound, a phosphate compound and an amide compound and comprises, as an essential component, a divalent or higher-valent aromatic polyvalent carboxylic acid.

Description

Method for producing polymer polyol and polyurethane

The present invention relates to a polymer polyol and a method for producing polyurethane using the polymer polyol. More specifically, the present invention relates to a polymer polyol that is suitable as a polyurethane raw material such as polyurethane foam and polyurethane elastomer and imparts excellent mechanical properties to polyurethane.

Conventionally, as a polymer polyol obtained by polymerizing an ethylenically unsaturated compound containing acrylonitrile in a polyol, acrylonitrile in the ethylenically unsaturated compound is used for the purpose of improving the scorch resistance of a polyurethane foam using the polymer polyol as a raw material. It is required to reduce the ratio (67 mol% or less). As a polymer polyol in which the acrylonitrile ratio in the polymer is lowered to increase the styrene ratio, a polymer polyol having a prescribed particle size distribution (see, for example, Patent Document 1) is known. Also known is a polymer polyol (see, for example, Patent Document 2) having a coarse particle concentration of 5 to 120 ppm having a diameter of 100 μm or more obtained by a continuous polymerization production method in which the dissolved oxygen concentration is controlled to 5 to 120 ppm.
On the other hand, there is a strong demand for cost reduction in recent years, and there is a demand for lowering the density of flexible polyurethane foam using a polymer polyol for weight reduction. For example, in a vehicle application, it is required to reduce the density of a flexible polyurethane foam for weight reduction corresponding to fuel consumption regulations.
In order to meet the demand for lower density, the amount of water used as a foaming agent tends to increase further. Increasing the amount of water used (Non-Patent Document 1, etc.) can increase the amount of carbon dioxide generated during foam production and is effective in reducing the density of flexible polyurethane foam. As the hardness decreases, the foam hardness decreases. As a specific technique for improving the hardness of the flexible polyurethane foam, there is a method of increasing the amount of the crosslinking agent to be used (Non-Patent Document 1), etc., but in such a method, the elongation and tensile strength of the flexible polyurethane foam are reduced. There remains a problem such as insufficient mechanical properties, and a flexible polyurethane foam is desired in which the hardness is improved and the mechanical properties are maintained.

Japanese Patent Laid-Open No. 11-236499 JP 2005-162791 A

An object of the present invention is to provide a polymer polyol capable of producing a polyurethane having a high tensile strength, and a method for producing a polyurethane using a polyol component containing the polymer polyol.

That is, the polymer polyol (I) of the present invention is a polymer polyol in which polymer fine particles (JR) having an ethylenically unsaturated compound (E) as a structural unit are contained in a polyol (PL), wherein (PL) is The gist is that it contains the following strength improver (b), and the volume average particle diameter (R) of (JR) is 0.1 to 1.5 μm.
Strength improver (b): at least one compound selected from the group consisting of an ester compound, a thioester compound, a phosphate ester compound, and an amide compound, wherein a divalent or higher aromatic polyvalent carboxylic acid is an essential constituent Further, the method for producing a polyurethane according to the present invention is a method for producing a polyurethane by reacting a polyol component and an isocyanate component, wherein the polyol component is based on the above-mentioned polymer polyol (I) based on the weight of the polyol component. The gist is to contain 100% by weight.

The polyurethane obtained using the polymer polyols (I) and (I) of the present invention has the following effects.
(1) The polyurethane foam produced using the polymer polyol (I) has improved mechanical properties such as improved hardness.

The polymer polyol of the present invention is a polymer (JR) obtained by polymerizing an ethylenically unsaturated compound (E) as a constituent unit and contained in the polyol (PL). As the ethylenically unsaturated compound (E), styrene (hereinafter abbreviated as St), acrylonitrile (hereinafter abbreviated as ACN), other ethylenically unsaturated monomers (e), and the like can be used. As an ethylenically unsaturated compound (E), it is preferable to make St and / or ACN into an essential component.

The proportion (% by weight) of St based on the total weight of the ethylenically unsaturated compound (E) constituting the polymer fine particles (JR) is preferably 60 to 100 from the viewpoint of discoloration of the polyurethane resin and the content of coarse particles. More preferably, it is 62 to 95, next more preferably 64 to 84, and most preferably 66 to 80.

The proportion (% by weight) of ACN based on the total weight of the ethylenically unsaturated compound (E) constituting the polymer fine particles (JR) is preferably 0 to 40 from the viewpoint of the content of coarse particles and discoloration of the polyurethane resin. More preferably, it is 5-38, then more preferably 16-36, most preferably 20-34.

The weight ratio of St to ACN (St: ACN) is preferably 100: 0 to 60:40, more preferably from the same viewpoint as the ratio of St and ACN in the ethylenically unsaturated compound (E). 95: 5 to 62:38, more preferably 84:16 to 64:36, and most preferably 80:20 to 66:34.

Other ethylenically unsaturated monomers (e) have 2 or more carbon atoms (hereinafter abbreviated as C) and a number average molecular weight (hereinafter abbreviated as Mn) [measurement is based on gel permeation chromatography (GPC) method. There is no particular limitation as long as it is less than 1,000 and can be copolymerized with St and / or ACN, and the following monofunctional ones [unsaturated nitrile (e1), aromatic ring-containing monomer (e2), ( (Meth) acrylic acid ester (e3), (poly) oxyalkylene ether of an α-alkenyl group-containing compound, and an alkylene oxide adduct (e4) of an unsaturated ester having a hydroxyl group, other ethylenically unsaturated monomers (e5)] And polyfunctional (2 or more) monomers (e6) and the like can be used. These may be used alone or in combination of two or more.

Examples of (e1) include methacrylonitrile.
Examples of (e2) include α-methylstyrene, hydroxystyrene, chlorostyrene and the like.
As (e3), methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl ( (Meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, etc. (meth) acrylic acid alkyl esters (alkyl group is C1-24) Hydroxypolyoxyalkylene (alkylene group is C2-8) mono (meth) acrylate and the like.
In addition, (meth) acrylate means methacrylate and / or acrylate, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, (meth) acrylic acid in the following, ( The same applies to (meth) allyl and the like, and the same notation is used hereinafter.

(E4) includes (poly) oxyalkylene ethers of α-alkenyl group-containing compounds and alkylene oxide adducts of unsaturated esters having a hydroxyl group.
The (poly) oxyalkylene ether of the α-alkenyl group-containing compound includes an alkylene oxide (hereinafter abbreviated as AO) adduct of a C3-24 unsaturated alcohol, and the unsaturated alcohol is preferably a terminal unsaturated alcohol. Used. Examples of the terminal unsaturated alcohol include allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, 1-hexen-3-ol and the like.
In addition, (poly) oxyalkylene ether means monooxyalkylene ether or polyoxyalkylene ether.

Examples of the AO adduct of an unsaturated ester having a hydroxyl group include an AO adduct of an unsaturated ester having a C3-24 hydroxyl group, and examples of the unsaturated compound ester having a hydroxyl group include hydroxyalkyl (C2-12) (meta ) Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like.

Among these, from the viewpoint of dispersion stability and viscosity, (poly) oxyalkylene ethers of α-alkenyl group-containing compounds are preferred, and AO adducts of allyl alcohol are more preferred. The number of moles of AO added is preferably 1 to 9, more preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of the physical properties of the polyurethane resin.
Examples of the AO include those having C2 to 12 or more, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-, 2 , 3- or 1,3-butylene oxide (hereinafter abbreviated as BO), tetrahydrofuran (hereinafter abbreviated as THF) and 3-methyl-tetrahydrofuran (hereinafter abbreviated as MTHF), 1,3-propylene oxide, Examples include isobutylene oxide, C5-12 α-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.), and combinations of two or more thereof (random addition and / or block addition).

AO is preferably C2 to 8 from the viewpoint of dispersion stability and viscosity, more preferably C2 to 4, particularly preferably C2 to 3, and most preferably PO and / or EO.
Moreover, as AO, from a viewpoint of dispersion stability and a viscosity, single use and combined use of 2 or more types of AO are preferable, More preferably, PO or EO is single and PO and EO are combined.

Mn of (e4) is preferably 110 to 490, more preferably 112 to 480, and still more preferably from the viewpoint of the low viscosity of the polymer polyol, the handleability of the polymer polyol and the hardness of the resulting polyurethane resin. 116 to 450, particularly preferably 170 to 420, and most preferably 180 to 300.

The number of unsaturated groups (α-alkenyl group or unsaturated ester group) in (e4) is 1 or more on average, and preferably 1 to 10 from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane resin described later. More preferably, the number is 1 to 2, particularly preferably 1.

The solubility parameter (hereinafter referred to as SP value) of (e4) is preferably 9.5 to 13, more preferably 9.8 to 12, from the viewpoint of the viscosity of the polymer polyol and the compression hardness of the polyurethane resin described later. .5, particularly preferably 10 to 12.2.
The SP value is represented by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.

SP value = (ΔE / V) ^1/2

Here, ΔE represents the cohesive energy density, V represents the molecular volume, and its value is Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

The other ethylenically unsaturated monomer (e5) is preferably a C2-24 ethylenically unsaturated monomer, for example, a vinyl group-containing carboxylic acid such as (meth) acrylic acid; an aliphatic hydrocarbon monomer such as ethylene or propylene; Fluorine-containing vinyl monomers such as perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate; Nitrogen-containing vinyl monomers other than unsaturated nitriles such as diaminoethyl methacrylate and morpholinoethyl methacrylate; Vinyl-modified silicones; Cyclic rings such as norbornene, cyclopentadiene and norbornadiene An olefin or a diene compound;

The polyfunctional monomer (e6) is preferably a C8-40 polyfunctional monomer such as divinylbenzene, ethylene di (meth) acrylate, polyalkylene oxide glycol di (meth) acrylate, pentaerythritol triallyl ether, trimethylolpropane tri. (Meth) acrylate etc. are mentioned.

Of (e1) to (e6), from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane resin, (e3) and (e6) are preferable, more preferably (e6), particularly preferably a bifunctional monomer, most preferably Divinylbenzene.

The proportion (mol%) of the other ethylenically unsaturated monomer (e) in the ethylenically unsaturated compound (E) constituting the polymer fine particles (JR) is preferably 40 or less, and the viscosity and dispersion stability of the polymer polyol From the viewpoint of the properties and physical properties of the polyurethane resin, it is more preferably 0.01 to 30, then more preferably 0.05 to 20, particularly preferably 0.1 to 15, and most preferably 0.2 to 10.
In particular, the use amount (% by weight) of (e4) is preferably 0 to 0.1, more preferably, based on the weight of (E), from the viewpoint of lowering the content of the soluble polymer and the physical properties of the polyurethane resin. Is from 0 to 0.05, more preferably from 0 to 0.01.

As the polyol (PL), known polyols used in the production of polymer polyols (Japanese Patent Application Laid-Open No. 2007-191682, Japanese Patent Application Laid-Open No. 2004-002800 (corresponding US Patent Application: US2005 / 245724A1), etc.) can be used. For example, a compound having a structure in which alkylene oxide is added to a compound (polyhydric alcohol, polyhydric phenol, amine, etc.) containing at least two (preferably 2 to 8 from the viewpoint of physical properties of the polyurethane resin) active hydrogen ( and a) and mixtures thereof. From the viewpoint of productivity at the time of polyurethane production, a compound having a structure in which an alkylene oxide is added to a polyhydric alcohol is preferable among these.

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

Examples of amines include alkanolamines, polyamines, and monoamines.
Examples of the alkanolamine include mono-, di- and tri-alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine).
Polyamines (number of primary, secondary amino groups: 2 to 8 or more) include aliphatic amines, alkylene diamines having 2 to 6 carbon atoms (for example, ethylene diamine, propylene diamine and hexamethylene diamine), carbon numbers 4-20 polyalkylene polyamines (dialkylene triamine, trialkylene tetramine, tetraalkylene pentamine, pentaalkylene hexamine and hexaalkylene heptamine whose alkylene group has 2 to 6 carbon atoms) and the like.
Also, aromatic polyamines having 6 to 20 carbon atoms (for example, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); alicyclic polyamines having 4 to 20 carbon atoms (for example, Isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine); heterocyclic polyamines having 4 to 20 carbon atoms (for example, piperazine and aminoethylpiperazine) and the like.
Monoamine as ammonia; aliphatic amine as alkylamine having 1 to 20 carbon atoms (for example, n-butylamine and octylamine); aromatic monoamine having 6 to 20 carbon atoms (for example, aniline and toluidine); -20 cycloaliphatic monoamines (eg, cyclohexylamine); C4-C20 heterocyclic monoamines (eg, piperidine), and the like.

Polyhydric (2 to 8 or higher) phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; condensates of phenol and formaldehyde (novolac) For example, polyphenols described in US Pat. No. 3,265,641.
Among these active hydrogen compounds, polyhydric alcohols are preferred from the viewpoint of mechanical properties of the resulting polyurethane resin.

The alkylene oxide to be added to the compound containing active hydrogen is preferably one having 2 to 8 carbon atoms from the viewpoint of the physical properties of the polyurethane resin, and includes EO, PO, 1,2-, 1,3-, 1,4- and Examples thereof include 2,3-BO, styrene oxide (hereinafter abbreviated as SO), and combinations of two or more thereof (block and / or random addition). From the viewpoint of the physical properties of the polyurethane resin, PO or a combination of PO and EO (EO content of 25% or less) is preferable. In the above and below, “%” means “% by weight” unless otherwise specified.

Specific examples of the polyol include known ones (Japanese Patent Laid-Open No. 2007-191682, etc.), and those obtained by adding PO to the active hydrogen-containing compound and PO and other AO, preferably EO The one added in the form of.
(1) Block added in the order of PO-AO (2) Block added in the order of PO-AO-PO-AO (3) Block added in the order of AO-PO-AO (4) PO- Block addition in the order of AO-PO (5) Random addition product in which PO and AO are mixed and added (6) Random or block addition in the order described in US Pat. No. 4,226,756 The hydroxyl group in (a) The equivalent is preferably 200 to 4,000, more preferably 400 to 3,000, from the viewpoint of the physical properties of the polyurethane resin. It is also preferable to use two or more types of (a) in combination so that the hydroxyl equivalent is within this range.

The strength improver (b) is at least one compound selected from the group consisting of an ester compound, a thioester compound, a phosphate ester compound, and an amide compound, and a divalent or higher aromatic polyvalent carboxylic acid is an essential constituent component. A compound having a structure represented by the following general formula (I) is preferable.

In general formula (I), R1 represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphate compound; a compound having two or more active hydrogen-containing functional groups in the molecule. These active hydrogen-containing compounds can be used either alone or in combination. That is, the plurality of R1s may be the same or different. Y represents a residue obtained by removing a carboxyl group from a trivalent or higher aromatic polycarboxylic acid. a is an integer satisfying 2 ≦ a ≦ the number of aromatic ring substituents−2. Z represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m. m represents an integer of 1 to 10.

Examples of the hydroxyl group-containing compound include monohydric alcohols, dihydric to octahydric polyhydric alcohols, phenols and polyhydric phenols. Specifically, monohydric alcohols such as methanol, ethanol, butanol, octanol, benzyl alcohol, naphthylethanol; ethylene glycol, propylene glycol, 1,3 and 1,4-butanediol, 1,6-hexanediol, 1, Dihydric alcohols such as 10-decanediol, diethylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene; glycerin and trimethylolpropane Trivalent alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl 4- to 8-valent alcohols such as lucoside and derivatives thereof: phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1, 3, 6 Phenol, such as 1,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil-based polyol; (co) heavy of hydroxyalkyl (meth) acrylate Examples thereof include polyfunctional polyols such as coalesced and polyvinyl alcohol (for example, 2 to 100 functional groups), condensates of phenol and formaldehyde (novolak), and polyphenols described in US Pat. No. 3,265,641.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

Examples of amino group-containing compounds include amines, polyamines and amino alcohols. Specific examples include ammonia; monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and anilines; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; and heterocyclic groups such as piperazine and N-aminoethylpiperazine. Polyamines; cycloaliphatic polyamines such as dicyclohexylmethanediamine and isophoronediamine; aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and dicarboxylic acids Polyamide polyamine obtained by condensation with excess polyamine; polyether polyamine; hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide ( Etc. Haq acid dihydrazide and dihydrazide terephthalate), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and the like.

Examples of the carboxyl group-containing compound include aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatic polycarboxylic acids such as succinic acid, fumaric acid, sebacic acid and adipic acid; phthalic acid , Isophthalic acid, terephthalic acid, trimellitic acid, naphthalene-1,4 dicarboxylic acid, naphthalene-2,3,6 tricarboxylic acid, pyromellitic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6- Examples thereof include aromatic polycarboxylic acids such as anthracentricarboxylic acid and pyrene dicarboxylic acid; polycarboxylic acid polymers (functional number 2 to 100) such as (co) polymers of acrylic acid, and the like.

Examples of the thiol group-containing compound include monofunctional phenylthiol, alkylthiol and polythiol compounds. Examples of the polythiol include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol and 1,6-hexanedithiol.

Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

As the active hydrogen-containing compound, a compound having two or more active hydrogen-containing functional groups (hydroxyl group, amino group, carboxyl group, thiol group, phosphate group, etc.) in the molecule can also be used.

Also, as the active hydrogen-containing compound, an alkylene oxide adduct of the active hydrogen-containing compound can also be used.

The alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen-containing compound includes AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO). Abbreviation), 1,3-propyloxide, 1,2-butylene oxide, 1,4-butylene oxide and the like. Of these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoints of properties and reactivity. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

Further, as the active hydrogen-containing compound, an active hydrogen-containing compound (polyester compound) obtained by a condensation reaction between the active hydrogen-containing compound and a polycarboxylic acid (aliphatic polycarboxylic acid or aromatic polycarboxylic acid) is used. Can do. In the condensation reaction, one type of active hydrogen-containing compound and polycarboxylic acid may be used, or two or more types may be used in combination.

The aliphatic polycarboxylic acid means a compound that satisfies the following (1) and (2).
(1) One molecule has two or more carboxyl groups.
(2) The carboxyl group is not directly bonded to the aromatic ring.

Examples of the aliphatic polycarboxylic acid include succinic acid, adipic acid, sebacic acid, maleic acid and fumaric acid.

The aromatic polycarboxylic acid means a compound satisfying the following (1) to (3).
(1) One molecule has one or more aromatic rings.
(2) The number of carboxyl groups in one molecule is 2 or more.
(3) The carboxyl group is directly bonded to the aromatic ring.

Aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 2,2'-bibenzyldicarboxylic acid, trimellitic acid, hemilitic acid, trimesic acid, pyromellitic acid and naphthalene-1,4 dicarboxylic acid, naphthalene And aromatic polycarboxylic acids having 8 to 18 carbon atoms such as -2,3,6 tricarboxylic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6-anthracentricarboxylic acid and pyrene dicarboxylic acid.

Also, when carrying out the condensation reaction between the polycarboxylic acid and the active hydrogen-containing compound, polycarboxylic acid anhydrides and lower alkyl esters can also be used.

From the viewpoint of handling the strength improver and improving the mechanical properties (elongation, tensile strength, compression hardness) of the polyurethane foam, the active hydrogen-containing compound R1 includes a hydroxyl group-containing compound, an amino group-containing compound, and these AO adducts. And a polyester compound obtained by a condensation reaction of an active hydrogen-containing compound and a polycarboxylic acid, more preferably methanol, ethanol, butanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitol, sucrose, benzyl alcohol, phenol , Methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine, phenylamine, diphenylamine, their EO and / or PO adducts and their active hydrogen compounds and phthalic acid Beauty / or condensate of isophthalic acid is preferred.

In general formula (I), Y represents a residue obtained by removing a carboxyl group from a trivalent or higher aromatic polycarboxylic acid (C). The aromatic ring of Y is composed of carbon atoms. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent is a hydrogen atom. That is, the aromatic ring of Y has at least one hydrogen atom bonded to the carbon atom constituting the aromatic ring.

Other substituents are alkyl group, vinyl group, allyl group, cycloalkyl group, halogen atom, amino group, carbonyl group, carboxyl group, hydroxyl group, hydroxyamino group, nitro group, phosphino group, thio group, thiol group Aldehyde group, ether group, aryl group, amide group, cyano group, urea group, urethane group, sulfone group, ester group and azo group. From the viewpoint of improving mechanical properties (elongation, tensile strength, compression hardness) and cost, the other substituents are preferably an alkyl group, a vinyl group, an allyl group, an amino group, an amide group, a urethane group and a urea group.

As the arrangement of substituents on Y, from the viewpoint of improving mechanical properties, two carbonyl groups are adjacent to each other, and hydrogen is arranged as a substituent between the third carbonyl group and the first or second carbonyl group. The structure is preferred.

Examples of trivalent or higher aromatic polycarboxylic acids (C) constituting Y include trimellitic acid, hemilitic acid, trimesic acid, pyromellitic acid, naphthalene-2,3,6 tricarboxylic acid and 2,3,6-anthracene. Examples thereof include aromatic polycarboxylic acids having 8 to 18 carbon atoms such as tricarboxylic acid.

From the viewpoint of handling the strength improver and improving the mechanical properties (tensile strength, tear strength, compression hardness) of the polyurethane foam, (C) used for Y is preferably a monocyclic compound, more preferably trimellitic acid and pyromellitic acid. It is merit acid.

A in the general formula (I) is an integer satisfying 2 ≦ a ≦ the number of aromatic ring substituents−2. The number of aromatic ring substituents is the number of substituents bonded to the carbon atoms constituting the aromatic ring. For example, a monocyclic aromatic ring composed of 6 carbons has 6 aromatic ring substituents, and a can take 2 to 4. When the aromatic ring is a monocyclic aromatic ring, a is preferably 2 or 3 from the viewpoint of improving mechanical properties (tensile strength, tear strength, compression hardness).

Z in the general formula (I) represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m. The active hydrogen-containing compound referred to here includes the active hydrogen-containing compound represented by R1 described above. However, the active hydrogen-containing compound represented by Z may be the same as a part of R1, but at least one R1 and Z must be different groups.
In the general formula (I), m represents an integer of 1 to 10.
From the viewpoint of handling the strength improver and improving the physical properties of the polyurethane foam (tensile strength, tear strength, compression hardness), Z includes a hydroxyl group-containing compound, an amino group-containing compound, an AO adduct thereof, and a polycarboxylic acid. A condensate with an acid is preferably used, and m is preferably 1-8.

The hydroxyl value (mgKOH / g) of the strength improver (b) is preferably from 0 to 700, more preferably from 0 to 650, and still more preferably from 0 to 700, from the viewpoint of handling (viscosity) and tensile strength during molding. 600.
Moreover, that the hydroxyl value of (b) is 0 means that none of R1, Y, and Z has a hydroxyl group in general formula (I).

The content of the strength improver (b) based on the weight of the polyol (PL) is preferably from 0.1 to 100% by weight, more preferably from 0.2 to 80% by weight, from the viewpoint of tensile strength and elongation properties. Particularly preferred is 0.5 to 60% by weight.

The polyol (PL) only needs to contain the strength improver (b), and when a strength improver other than (b) is used, the production method of (PL) is a strength improver other than (b). And a method of mixing (b).

The polymer polyol (I) of the present invention is a polymer polyol in which polymer fine particles (JR) having an ethylenically unsaturated compound (E) as a structural unit are contained in the polyol (PL).

The shape of the polymer fine particles (JR) is not particularly limited, and may be any shape such as a spherical shape, a spheroid shape, and a flat plate shape, but a spherical shape is preferable from the viewpoint of mechanical properties of the polyurethane resin.

The volume average particle diameter (R) (μm) of the polymer fine particles (JR) is 0.1 to 1.5, preferably 0.1 to 0.9, from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane resin. More preferably, it is 0.25 to 0.8, then more preferably 0.3 to 0.7, and particularly preferably 0.4 to 0.6. When the volume average particle diameter (R) of the polymer fine particles (JR) is less than 0.1, the viscosity increases and handling is deteriorated. When the volume average particle diameter (R) of the polymer fine particles (JR) exceeds 1.5, the hardness and cutting elongation of the polyurethane are lowered.
The volume average particle diameter is measured by the method described later.

The polymer fine particle content (% by weight) in the polymer polyol (I) is preferably 10 to 50 from the viewpoint of mechanical properties of the polyurethane resin described later and prevention of aggregation of the polymer fine particles (JR) in the polymer polyol. Preferably it is 10 to 45, particularly preferably 12 to 40, most preferably 15 to 35.
In addition, polymer fine particle content (weight%) is measured by the method mentioned later.

The content (% by weight) of the polyol (PL) in the polymer polyol (I) is preferably 50 to 90, more preferably from the viewpoint of preventing aggregation of the polymer fine particles (JR) and mechanical properties of the resulting polyurethane resin. 55 to 90, particularly preferably 60 to 88, and most preferably 65 to 85.

The ratio (soluble polymer content / polymer fine particle content) of the soluble polymer content (% by weight) and the polymer fine particle content (% by weight) in the polymer polyol (I) is the polymer fine particles in the polymer polyol. Is preferably 1/10 or less, more preferably 2.5 / 30 or less, and even more preferably 2/30 or less, from the viewpoint of reducing the particle size of the polyurethane resin, the mechanical properties of the resulting polyurethane resin, and the viscosity of the polymer polyol. Especially preferably, it is 1.5 / 30 or less. The soluble polymer content is measured by the following method.

<Method for measuring soluble polymer content (% by weight)>
(Measurement of methanol precipitate content)
In a 50 ml centrifuge tube for centrifugation, about 5 g of polymer polyol is precisely weighed to obtain the polymer polyol weight (W1). Add 50 g of methanol and mix. Using a cooling centrifuge [model number: H-9R, manufactured by Kokusan Co., Ltd.], centrifuge at 18,000 rpm for 60 minutes at 20 ° C. The supernatant is removed using a glass pipette. The operation of adding 50 g of methanol to the residual sediment, mixing, and centrifuging in the same manner as above to remove the supernatant is repeated three more times. The residual sediment in the centrifuge tube is dried under reduced pressure at 2,666 to 3,999 Pa (20 to 30 torr) at 60 ° C. for 60 minutes, and the dried sediment is weighed to obtain (W2). The value calculated by the following formula is defined as the methanol precipitate content (% by weight).

Methanol precipitate content (% by weight) = (W2) × 100 / (W1)

(Measurement of xylene precipitate content)
Next, about 5 g of polymer polyol is precisely weighed in a 50 ml centrifuge tube for centrifugal separation to obtain the weight of polymer polyol (W3). Add 50 g of xylene and mix. Using a cooling centrifuge [model number: H-9R, manufactured by Kokusan Co., Ltd.], centrifuge at 18,000 rpm for 60 minutes at 20 ° C. The supernatant is removed using a glass pipette. The operation of adding 50 g of xylene to the remaining sediment, mixing, and centrifuging in the same manner as above to remove the supernatant is repeated three more times. The residual sediment in the centrifuge tube is dried under reduced pressure at 2,666-3,999 Pa (20-30 torr) at 60 ° C. for 60 minutes, the dried sediment is weighed, and the weight is defined as (W4). The value calculated by the following formula is the xylene precipitate content (% by weight).

Xylene precipitate content (% by weight) = (W4) × 100 / (W3)

(Calculation of soluble polymer content)
The value calculated by the following formula is defined as the soluble polymer content (% by weight).

Soluble polymer content (wt%) = methanol precipitate content (wt%)-xylene precipitated granule content (wt%)

Polymer fine particle content (% by weight) is measured by the following method.

<Polymer fine particle content (% by weight)>
In a 50 ml centrifuge tube for centrifugation, about 5 g of polymer polyol is precisely weighed to obtain the polymer polyol weight (W5). Add 50 g of methanol and mix. Using a cooling centrifuge [model number: H-9R, manufactured by Kokusan Co., Ltd.], centrifuge at 18,000 rpm for 60 minutes at 20 ° C. The supernatant is removed using a glass pipette. The operation of adding 50 g of methanol to the residual sediment, mixing, and centrifuging in the same manner as above to remove the supernatant is repeated three more times. The residual sediment in the centrifuge tube is dried under reduced pressure at 2,666-3,999 Pa (20-30 torr) at 60 ° C. for 60 minutes. The value calculated by the following formula is defined as the polymer fine particle content (% by weight).

Polymer fine particle content (% by weight) = (W6) × 100 / (W5)

The soluble polymer means a polymer that does not dissolve in methanol but dissolves in xylene in the above measurement method. When the content of the soluble polymer is large, the viscosity of the polymer polyol is increased and the handling tends to be deteriorated. Further, since the content of particulate polymer fine particles (= polymer fine particle content−soluble polymer content) that contributes to foam hardness is reduced, the physical properties of the foam tend to be deteriorated.
The ratio of soluble polymer content (% by weight) to polymer fine particle content (% by weight) (soluble polymer content / polymer fine particle content) means the weight ratio of this soluble polymer to polymer fine particles. When the weight ratio is large, the viscosity of the polymer polyol increases, and the handling tends to deteriorate. Further, since the content of particulate polymer fine particles (= polymer fine particle content−soluble polymer content) that contributes to foam hardness is reduced, the physical properties of the foam tend to be deteriorated.

In the present invention, the arithmetic standard deviation of the particle diameter of the polymer fine particles (JR) is 0.6 or less from the viewpoint of ease of production of the polymer polyol, mechanical properties of the polyurethane resin and reduction of clogging of the polyurethane resin production apparatus. More preferably, it is 0.1 to 0.6, next more preferably 0.12 to 0.6, particularly preferably 0.15 to 0.6, and most preferably 0.20 to 0.58. . The arithmetic standard deviation is an arithmetic standard deviation based on volume and is measured by a method described later.

The above-mentioned arithmetic standard deviation based on the volume refers to the arithmetic standard deviation calculated by the following formula from the particle size distribution based on the volume based on the Mie scattering theory (Light Scattering by Small Particles, Dover Publ., 1981). Note that the volume-based particle size distribution in the measurement and calculation is a range of 0.040 to 262 μm divided into 65 (0.040 to 0.044 μm, 0.044 to 0.050 μm, 0.051 to 0.057 μm,. 058-0.066μm, 0.067-0.075μm, 0.076-0.086μm, 0.087-0.099μm, 0.100-0.114μm, 0.115-0.130μm, 0.131- 0.149 μm, 0.150 to 0.171 μm, 0.172 to 0.196 μm, 0.197 to 0.225 μm, 0.226 to 0.258 μm, 0.259 to 0.295 μm, 0.296 to 0. 338 μm, 0.339 to 0.388 μm, 0.389 to 0.449 μm, 0.450 to 0.509 μm, 0.510 to 0.583 μm, 0.584 to 0.668 μm, 69 to 0.765 μm, 0.766 to 0.876 μm, 0.877 to 1.004 μm, 1.005 to 1.150 μm, 1.151 to 1.317 μm, 1.318 to 1.509 μm, 1,510 to 1.728 μm, 1.729 to 1.980 μm, 1.981 to 2.268 μm, 2.269 to 2.598 μm, 2.599 to 2.975 μm, 2.976 to 3.408 μm, 3.409 to 3. 904 μm, 3.905 to 4.471 μm, 4.472 to 5.121 μm, 5.122 to 5.866 μm, 5.867 to 6.719 μm, 6.720 to 7.696 μm, 7.697 to 8.815 μm, 8.816 to 10.096 μm, 10.097 to 11.564 μm, 11.565 to 13.245 μm, 13.246 to 15.171 μm, 15.172 to 17.376 μm 17.377-19.903 μm, 19.904-22.796 μm, 22.797-26.110 μm, 26.111-29.906 μm, 29.907-34.254 μm, 34.255-39.233 μm, 39 .234 to 44.937 μm, 44.938 to 51.470 μm, 51.471 to 58.952 μm, 58.953 to 67.522 μm, 67.523 to 77.338 μm, 77.339 to 88.582 μm, 88.583 ˜101.594 μm, 101.460 to 116.209 μm, 116.210 to 133.102 μm, 133.103 to 152.452 μm, 152.453 to 174.615 μm, 174.616 to 199.999 μm, 200.000 to 229 074 μm, 229.075 to 262.375 μm, 65 divisions . For example, the description “0.040 to 0.044 μm” indicates “greater than 0.040 μm and 0.044 μm or less”. )

Arithmetic standard deviation = [Σ {(X (J) −arithmetic mean particle diameter (μm)} ² × q (J) / 100] ^1/2

Arithmetic mean particle diameter (μm) = Σ {q (J) × X (J)} / Σ {q (J)}

In the formula, J is a particle size range division number (1 to 65), that is, a particle size range number sequentially numbered from the smallest value of the 65 divided particle size range; X (J) is The center value of the particle number range of the division number Jth; q (J) is the frequency (volume%) of particles in the particle number range of the division number Jth.

The content (% by weight) of polymer fine particles having a particle diameter of 0.10 mm or more in the polymer polyol (I) (hereinafter abbreviated as coarse particle content) is from the viewpoint of reducing clogging in a polyurethane resin production apparatus. Based on the weight of the polymer polyol (I), 0 to 30 × 10 ⁻⁴ is preferable, more preferably 0 to 20 × 10 ⁻⁴ , next more preferably 0 to 10 × 10 ⁻⁴ , particularly preferably 0. ~ 3 × 10 ^-4 .

The polymer polyol (I) of the present invention can be obtained by a method of producing by polymerizing an ethylenically unsaturated compound (E) in a polyol (PL).

This production method is a method of polymerizing the ethylenically unsaturated compound (E) in a dispersion medium containing a polyol (PL).
Examples of the polymerization method include radical polymerization, coordination anion polymerization, metathesis polymerization, Diels-Alder polymerization, and the like. From an industrial viewpoint, radical polymerization is preferable.

Radical polymerization can be performed by various methods, for example, a method of polymerizing an ethylenically unsaturated compound (E) in the presence of a radical polymerization initiator (c) in a polyol (PL) containing a dispersant (d) (US Pat. The method described in Japanese Patent No. 3383351 etc. can be used.

As the radical polymerization initiator (c), a compound that generates a free radical to initiate polymerization can be used, such as an azo compound and a peroxide {Japanese Patent Laid-Open No. 2005-162791, Japanese Patent Laid-Open No. 2004-002800 (corresponding to US patent application: US2005 / 245724 A1) etc.} can be used. The 10-hour half-life temperature of (c) is preferably from 30 to 150 ° C., more preferably from 40 to 140 ° C., particularly preferably from the viewpoint of the polymerization rate and polymerization time of (E) and the productivity of the polymer polyol. 50-130 ° C.

The amount (% by weight) used of (c) is preferably 0.05 to 20, more preferably from the viewpoint of the degree of polymerization of (E) and the mechanical properties of the resulting polyurethane resin, based on the total weight of (E). It is 0.1 to 5, particularly preferably 0.2 to 2.

As the dispersant (d), various dispersants having an Mn of 1,000 or more (preferably 1,000 to 10,000), for example, known dispersants used in the production of polymer polyols {Japanese Patent Laid-Open No. 2005-162791 And the like described in JP 2004-002800 A (corresponding US Patent Application: US 2005/245724 A1), etc., and (d) is ethylene that can be copolymerized with St or ACN. Reactive dispersants having ionic unsaturated groups, and non-reactive dispersants that do not copolymerize with St or ACN.
In the present invention, the reactive dispersant containing an ethylenically unsaturated group has a Mn of 1,000 or more, and is distinguished from an ethylenically unsaturated compound (E) having a Mn of less than 1,000.

Specific examples of the dispersant (d) include: [1] At least a part of the hydroxyl group of the polyol is reacted with methylene dihalide and / or ethylene dihalide to obtain a high molecular weight, and the reaction product is further mixed with an ethylenically unsaturated group. Ethylenically unsaturated group-containing modified polyol obtained by reacting a compound containing compound (such as those described in JP 08-333508 A, JP 2004-002800 A (corresponding US patent application: US 2005/245724 A1), etc.) Macromer type dispersant; [2] The difference in solubility parameter from the polymer of the ethylenically unsaturated compound is 2 with two or more polyol affinity segments having a solubility parameter difference of 1.0 or less as a side chain. 0.0 or less polymer fine particle (JR) graft polymer having an affinity segment as a main chain (Japanese Patent Laid-Open No. 05-05913) A graft type dispersant in which a polyol and an oligomer are bonded, such as those described in Japanese Patent No. 4); and [3] at least a part of the hydroxyl group of the polyol is reacted with methylene dihalide and / or ethylene dihalide. High molecular weight polyol type dispersants such as molecular weight modified polyols (as described in JP-A-07-196749 etc.); [4] Mn is 1,000 to 1,000,000, at least a part thereof Oligomeric type dispersions such as vinyl oligomers, which are soluble in polyols, and dispersants (for example, JP-A-09-77968) that use the oligomers together with the above-mentioned [1] modified polyether polyols containing ethylenically unsaturated groups Agent. Including (d1) described later}; [5] A nitrogen-containing unsaturated polyol containing a polyol and a monofunctional active hydrogen compound having at least one ethylenically unsaturated group bonded via a polyisocyanate. Reactive dispersants {including (d2) to be described later} such as a dispersant (described in JP-A-2002-308920 (corresponding to US Pat. No. 6,756,414)) and the like.
Among these, [1], [4] and [5] are preferable, and [5] is more preferable from the viewpoint of the particle diameter of the polymer fine particles (JR).

Of these, the following (d1) and / or (d2) are particularly preferred from the viewpoint of the particle diameter of the polymer fine particles (JR).
(D1) Vinyl oligomer having Mn of 1,000 to 1,000,000.
(D2) A saturated polyol (p) and a monofunctional active hydrogen-containing compound (q) having at least one ethylenically unsaturated group are bonded via a polyisocyanate (r), A nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups of 0.1 to 0.4.

The dispersant (d1) is a vinyl oligomer obtained by polymerizing an ethylenically unsaturated compound. As the ethylenically unsaturated compound constituting the dispersant (d1), the same ethylenically unsaturated compound (E) as described above can be used.
Among these, at least a part of the ethylenically unsaturated compound constituting the dispersant (d1) from the viewpoint of the particle diameter of the polymer fine particles (JR) is an ethylenically unsaturated compound ( It is preferred that it is the same as E), more preferably 30% by weight or more of the ethylenically unsaturated compound constituting (d1) is the same as (E), then more preferably 70% by weight or more, particularly preferably Is 80% by weight or more.

Mn in (d1) is 1,000 to 1,000,000, preferably 100,000 to 950,000, more preferably 150,000 to 900,000, from the viewpoint of the particle size of the polymer particles. Particularly preferred is 200,000 to 250,000. Further, the dispersant (d1) is soluble in the polyol (PL) from the viewpoint of the particle size of the polymer fine particles [5% by weight of (d1) and (PL) are uniformly converted to (PL) based on the total weight of (d1) and (PL). It is desirable that the laser transmittance of the mixed mixture is 10% or more.
In addition, Mn of a dispersing agent (d1) is measured with the following method.
About 5 g of polymer polyol is precisely weighed in a 50 ml centrifuge tube for centrifugation, and diluted by adding 50 g of methanol. Using a cooling centrifuge [model number: H-9R, manufactured by Kokusan Co., Ltd.], centrifuge at 18,000 rpm for 60 minutes at 20 ° C. The supernatant is removed using a glass pipette. The operation of adding 50 g of methanol to the residual sediment, diluting, and centrifuging in the same manner as above to remove the supernatant is repeated three more times. The residual sediment in the centrifuge tube is dried under reduced pressure at 2,666-3,999 Pa (20-30 torr) at 60 ° C. for 60 minutes to obtain a dried sediment. The number average molecular weight is measured on the basis of polystyrene by gel permeation chromatography (GPC) measurement of this sediment, and is defined as Mn of (d1).

The dispersant (d1) can be produced by a normal polymerization method of an ethylenically unsaturated compound, except that the degree of polymerization is adjusted so that Mn is 1,000 to 1,000,000. For example, it is a method in which the ethylenically unsaturated compound (E) is polymerized in the presence of a radical polymerization initiator (c) described later, if necessary, in a solvent. The dispersant (d1) may be obtained by polymerizing (E) in the polyol (PL). In this case, the polymerization concentration is preferably 1 to 40% by weight, more preferably 5 to 20% by weight. is there. You may use for the production of a polymer polyol as it is, without refine | purifying what was obtained by superposition | polymerization. The radical polymerization initiator is used in a relatively large amount, for example, preferably 2 to 30% by weight, more preferably 5 to 20% by weight, based on the weight of the total ethylenically unsaturated compound.

Solvents used as necessary for the polymerization reaction include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, isopropyl alcohol, n-butanol and the like. Can be mentioned.
Of these solvents, toluene, xylene, isopropyl alcohol and n-butanol are preferred from the viewpoint of viscosity and mechanical strength of the polyurethane resin to be produced.

If necessary, chain transfer agents such as alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, etc.), halogenated hydrocarbons (carbon tetrachloride, carbon tetrabromide, chloroform, etc.) And polymerization in the presence of an enol ether described in JP-A-55-31880. The polymerization can be carried out either batchwise or continuously. The polymerization reaction can be performed at a temperature equal to or higher than the decomposition temperature of the radical polymerization initiator (usually 50 to 250 ° C., preferably 80 to 200 ° C., particularly preferably 100 to 180 ° C.), and can be performed under atmospheric pressure or under pressure. Can do.

(D2) is formed by bonding a saturated polyol (p) and a monofunctional active hydrogen compound (q) having at least one ethylenically unsaturated group via a polyisocyanate (r). The nitrogen-containing bond-containing unsaturated polyol has an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups of 0.1 to 0.4.

As (p) constituting (d2), the same as those exemplified as the (PL) can be used. (P) and (PL) may be the same or different.
The number of hydroxyl groups in one molecule of (p) is preferably at least 2, from the viewpoint of dispersion stability of the polymer fine particles (JR) in (PL), more preferably 2-8, and further The number of hydroxyl groups in (p) is preferably from 1,000 to 3,000, more preferably from 1,500 to 2,500, from the viewpoint of dispersion stability.

(Q) used to obtain (d2) is a compound having one active hydrogen-containing group and at least one polymerizable unsaturated group. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, an imino group, a carboxyl group, and an SH group, and a hydroxyl group is particularly preferable from the viewpoint of polymer particle stability.

The ethylenically unsaturated group of (q) is preferably a polymerizable double bond from the viewpoint of being easily incorporated into the polymer forming the polymer fine particles, and the number of ethylenically unsaturated groups in one molecule is 1 to 3. In particular, one is preferable. That is, preferred as (q) is an unsaturated monohydroxy compound having one polymerizable double bond.
Examples of the unsaturated monohydroxy compound include monohydroxy substituted unsaturated hydrocarbon, monoester of unsaturated monocarboxylic acid and dihydric alcohol, monoester of unsaturated dihydric alcohol and monocarboxylic acid, alkenyl side chain Examples thereof include phenol having a group and unsaturated polyether monool.

Monohydroxy substituted unsaturated hydrocarbons include C3-6 alkenols such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol and the like; alkynol, An example is propargyl alcohol.
Examples of monoesters of unsaturated monocarboxylic acids and dihydric alcohols include C3-8 unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, and dihydric alcohols (ethylene glycol, Monoesters with C2-12 dihydric alcohols such as propylene glycol and butylene glycol), and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy Examples thereof include propyl methacrylate, 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate.

Examples of the monoester of unsaturated dihydric alcohol and monocarboxylic acid include monoesters of C3-8 unsaturated dihydric alcohol and C2-12 monocarboxylic acid, such as acetic acid monoester of butenediol.
Examples of the phenol having an alkenyl side chain group include phenols having an alkenyl side chain group in which C of the alkenyl group is 2 to 8, such as oxystyrene and hydroxy α-methylstyrene.
Examples of the unsaturated polyether monool include adducts of 1 to 50 moles of the above monohydroxy-substituted unsaturated hydrocarbon or alkylene oxide (C2 to 8) of phenol having an alkenyl side group [for example, polyoxyethylene (degree of polymerization 2 to 2). 10) monoallyl ether] and the like.

Examples of (q) other than the unsaturated monohydroxy compound include the following.
Examples of (q) having an amino group or imino group include mono- and di- (meth) allylamine, aminoalkyl (C2-4) (meth) acrylate [aminoethyl (meth) acrylate, etc.], monoalkyl (C1-12) ) Aminoalkyl (C2-4) (meth) acrylate [monomethylaminoethyl-methacrylate and the like]; (q) having a carboxyl group is the above unsaturated monocarboxylic acid; (q) having an SH group is And compounds corresponding to saturated monohydroxy compounds (OH is replaced by SH). Examples of (q) having two or more polymerizable unsaturated groups include poly (meth) allyl ethers of trihydric, tetrahydric, octahydric or higher polyhydric alcohols or polyesters with unsaturated carboxylic acids [ Examples thereof include trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, and the like.

From the viewpoint of dispersion stability, preferred compounds among these include C3-6 alkenols, monoesters of C3-8 unsaturated monocarboxylic acids and C2-12 dihydric alcohols, and phenols having alkenyl side groups. More preferably, monoesters of (meth) acrylic acid with ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, particularly preferably 2-hydroxyethyl (meth) acrylate. .
Further, the molecular weight of (q) is not particularly limited, but is preferably 1,000 or less, and particularly preferably 500 or less, from the viewpoint of the viscosity of the polymer polyol.

The polyisocyanate (r) is a compound having at least two isocyanate groups. The aromatic polyisocyanate (r1), the aliphatic polyisocyanate (r2), the alicyclic polyisocyanate (r3), the araliphatic polyisocyanate ( r4), modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups or oxazolidone group-containing modified products) (r5), and mixtures of two or more thereof Is mentioned.

Examples of (r1) include C (excluding carbon in the NCO group; the same applies to the following polyisocyanates) 6 to 16 aromatic diisocyanates, C6 to 20 aromatic triisocyanates, and crude products of these isocyanates. . Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4,4 ′. Diphenylmethane diisocyanate (MDI), crude MDI [crude diaminodiphenylmethane {condensation product of formaldehyde and aromatic amine (aniline); small amount of diaminodiphenylmethane as main product and a small amount of by-product (eg 5 to 20% by weight) Phosgenates of mixtures of polyamines with three or more functional groups: for example, polyallyl polyisocyanate (PAPI), etc.], naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, etc. It is done.
Examples of (r2) include C2-18 aliphatic diisocyanates. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

Examples of (r3) include C4-16 alicyclic diisocyanates. Specific examples include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of (r4) include C8-15 araliphatic diisocyanates. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Examples of (r5) include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
From the viewpoint of the physical properties of the polyurethane resin, aromatic diisocyanates are preferable among these, and 2,4- and / or 2,6-TDI are more preferable.

The nitrogen-containing bond of (d2) is generated by a reaction between an isocyanate group and an active hydrogen-containing group. When the active hydrogen-containing group is a hydroxyl group, a urethane bond is mainly generated, and when it is an amino group, A urea bond is formed in In the case of a carboxyl group, an amide bond is formed, and in the case of an SH group, a thiourethane bond is formed. In addition to these groups, other bonds such as a burette bond and an allophanate bond may be formed.
This nitrogen-containing bond is generated by the reaction between the hydroxyl group of the saturated polyol (p) and the isocyanate group of the polyisocyanate (r), the active hydrogen-containing group of the unsaturated monofunctional active hydrogen compound (q), and (r). Some are produced by reaction with isocyanate groups.

(D2) is a ratio obtained by the following formula so that the average ratio of the number of unsaturated groups to nitrogen-containing bonds derived from the NCO group of (r) in one molecule is 0.1 to 0.4. , (P), (q) and (r) are reacted.
Average value of the ratio of the number of unsaturated groups to nitrogen-containing bonds derived from the (r) NCO group in one molecule =
[Number of moles of (q) × number of unsaturated groups of (q)] / [number of moles of (r) × number of NCO groups of (r)]
The average value of the ratio of the number of unsaturated groups to nitrogen-containing bonds derived from the (r) NCO group in one molecule is more preferably 0.1 to 0.3, particularly preferably 0.2 to 0. .3. When the average value of the ratio of the number of unsaturated groups is within the above range, the dispersion stability of the polymer polyol is particularly good.

The content of the dispersant (d) is preferably 50% by weight or less based on the weight of (E), from the viewpoint of the particle diameter of the polymer fine particles (JR) and the viscosity of the resulting polymer polyol, Preferably it is 1 to 40% by weight, then more preferably 1 to 30% by weight, particularly preferably 3 to 25% by weight, most preferably 5 to 20% by weight.

In radical polymerization, a diluting solvent (f) may be used if necessary. (F) includes aromatic hydrocarbons (C6-10, such as toluene, xylene); saturated aliphatic hydrocarbons (C5-15, such as hexane, heptane, normal decane); unsaturated aliphatic hydrocarbons (C5-30). For example, octene, nonene, decene); and other known solvents (for example, those described in JP-A-2005-162791, etc.) can be used. Of these, aromatic hydrocarbon solvents are preferred from the viewpoint of the viscosity of the polymer polyol.
The use amount (% by weight) of the diluting solvent (f) is preferably 0.1 to 50 based on the total weight of the ethylenically unsaturated compound (E) from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane resin. More preferably, it is 1 to 40. Although (f) may remain in the polymer polyol after the completion of the polymerization reaction, it is desirable to remove by vacuum stripping after the polymerization reaction from the viewpoint of the mechanical properties of the polyurethane resin.

In radical polymerization, a chain transfer agent (g) may be used if necessary. Examples of (g) include various chain transfer agents such as aliphatic thiols (C1-20, such as n-dodecanethiol, mercaptoethanol) (Japanese Patent Laid-Open No. 2005-162791, Japanese Patent Laid-Open No. 2004-002800 (corresponding US patent application: US2005 / 245724 A1) etc.} can be used.
The amount (% by weight) of the chain transfer agent (g) is preferably 0.01 from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the resulting polyurethane resin, based on the total weight of the ethylenically unsaturated compound (E). ˜2, more preferably 0.1˜1.

The production method for obtaining the polymer polyol (I) of the present invention includes the following steps (1) and (n) from the viewpoint of the viscosity of the polymer polyol and the volume average particle diameter of the polymer fine particles. The method is preferred.
Step (1): Ethylenic unsaturation in (PL) in the presence of fine particles (P1) and a radical polymerization initiator (c), and optionally in the presence of a dispersant (d) and / or a diluting solvent (f). Step (n) for polymerizing compound (E) to obtain polymer polyol intermediate (B1): In polymer polyol intermediate (B (n-1)), in the presence of (c), if necessary (d) And / or (f) is polymerized to obtain a polymer polyol intermediate (B (n)) or polymer polyol (I) by polymerizing (E) (n represents an integer of 2 to 6).

N is an integer of 2 to 6, preferably an integer of 2 to 4, more preferably an integer of 2 to 3, from the viewpoint of the particle diameter of the polymer. When n is 7 or more, the viscosity of (I) increases. When n is 1 or less, it means that the step (n) is not included, but in this case, the volume average particle diameter (R) of the polymer fine particles is increased, and the properties of the produced polyurethane resin are deteriorated.

In the step (1), the concentration (% by weight) of the ethylenically unsaturated monomer (E) based on the total weight of (PL), (P1), (E), (c), (d) and (f) Is preferably from 7 to 40, more preferably from 10 to 35, and even more preferably from 15 to 30 from the viewpoint of the physical properties of the polyurethane resin and the particle diameter of the polymer.

In step (1), the content (% by weight) of (P1) based on the total weight of (PL), (P1), (E), (c), (d) and (f) and the step (1) )) (E) concentration ratio, from the viewpoint of the physical properties of the polyurethane resin and the particle diameter of the polymer, the (P1) content in step (1): (E) concentration in step (1) = 30: 7 to 7:40, more preferably 25:10 to 10:35, and particularly preferably 20:30 to 12:15.

From the viewpoint of productivity, the lower limit of the conversion rate (% by weight) of the polymer (E) in the step (1) is preferably 75% or more, more preferably 80% or more, and particularly preferably 85% or more. From the viewpoint of the particle diameter of the polymer, the upper limit is preferably 99.5% or less, more preferably 99.2% or less, and particularly preferably 99% or less.

In step (n), the ethylenically unsaturated monomer (E) based on the total weight of the polymer polyol intermediates (B (n-1)), (E), (c), (d) and (f) The concentration is preferably from 7 to 40, more preferably from 10 to 35, and particularly preferably from 15 to 30 from the viewpoint of the physical properties of the polyurethane resin and the viscosity of the resulting polymer polyol.
Note that the concentration of (E) in step (n) is the same as that of (E) included in (B (n-1)) when (E) is included in (B (n-1)). The concentration is to be calculated.
Further, in step (n), polyol (PL) may be further added. In that case, the concentration is calculated by adding the added (PL).

From the viewpoint of productivity, the lower limit of the conversion rate (% by weight) of the polymer (E) in the step (n) is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. From the viewpoint of the particle diameter of the polymer, the upper limit is preferably 99.5% or less, more preferably 99.2% or less, and particularly preferably 99% or less.

The polymerization temperature (° C.) is preferably from 100 to 180, more preferably from 110 to 160, particularly preferably from 120 to 140, from the viewpoint of productivity and prevention of polyol decomposition.

In step (1) and step (n), the polymerization method may be any method such as continuous polymerization, batch polymerization (drop polymerization, batch polymerization, etc.). From the viewpoint of productivity, the continuous polymerization method or batch batch polymerization method is preferable.
Moreover, the polymerization methods in the step (1) and the step (n) may be the same or different.

The polymer polyol intermediate (B (n)) obtained in the step (n) may be used as it is as the polymer polyol (I), or the polymer polyol (I) may be obtained by carrying out a monomer removal / solvent removal treatment if necessary. . From the viewpoint of the odor of the polyurethane resin, it is preferable to perform a monomer removal treatment and a solvent removal treatment.

The fine particles (P1) are not particularly limited as long as they are inorganic or organic particulate substances, and may be used alone or in combination of two or more depending on the purpose. That is, any of inorganic fine particles (PA1), organic fine particles (PA2), and combinations of (PA1) and (PA2) may be used.

Examples of the inorganic fine particles (PA1) include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, Metal oxides such as samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrite, metal hydroxide such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, hydrotalcite , Heavy calcium carbonate, light calcium carbonate, metal carbonate such as zinc carbonate, barium carbonate, dawsonite, metal sulfate such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, clay , Ta , Mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes and other metal silicates, aluminum nitride, boron nitride, silicon nitride and other metal nitrides, potassium titanate, Metal titanates such as calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphates such as tricalcium phosphate, Inorganic particles such as metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbon such as carbon black, graphite and carbon fiber, metals such as gold and silver, and the like. (PA1) may be used alone or in combination of two or more depending on the purpose.
(PA1) includes metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal titanate, metal borate, metal phosphate, metal sulfide, carbon Is preferred.

Examples of the organic fine particles (PA2) include vinyl resins, urethane resins, epoxy resins, polyester resins, polyamides, polyimides, silicone resins, fluorine resins, phenol resins, melamine resins, benzoguanamine resins, urea resins, aniline resins, ionomer resins, Well-known organic resin microparticles | fine-particles (PA21), such as a polycarbonate, a cellulose, and these mixtures, are mentioned. Organic waxes such as ester wax (carnauba wax, montan wax, rice wax, etc.), polyolefin wax (polyethylene, polypropylene, etc.), paraffin wax, ketone wax, ether wax, long-chain aliphatic alcohol, long-chain fatty acid and mixtures thereof Fine particle (PA22), metal salt fine particle of long chain fatty acid (PA23) and the like. Moreover, fine particles of various organic dyes or organic pigments such as azo compounds, phthalocyanines, condensed polycyclic compounds and dye lakes generally used as colorants can be used. (PA2) may be used alone or in combination of two or more depending on the purpose.
(PA2) is preferably a vinyl resin, a urethane resin, an epoxy resin, a polyester resin, a fluororesin, a silicone resin, a melamine resin, or a benzoguanamine resin.

The fine particles (P1) may be used as they are, and surface treatment with a coupling agent such as silane, titanate, aluminate or the like (for example, a method described in JP-A-11-130979) in order to impart the adsorptivity of the polymer. Etc.), surface modification with various surfactants (methods described in JP-A-8-54752), coating treatment with wax or polymer (methods described in JP-A-2006-328261, etc.), etc. May be.

The fine particles (P1) are preferably (PA1), (PA21), (PA23), and a mixture of two or more thereof.
More preferred are metal oxides, metal carbonates, metal silicates and (PA21), and still more preferably silica, diatomaceous earth, heavy calcium carbonate, light calcium carbonate, kaolin, clay, talc, mica, bentonite, Activated clay, urethane resin, vinyl resin and polyester resin, particularly preferably silica, heavy calcium carbonate, light calcium carbonate, diatomaceous earth, talc, clay, activated clay, vinyl resin, most preferably ethylenic It is a polymer obtained by polymerizing the saturated compound (E).

The volume average particle diameter (R1) of the fine particles (P1) is preferably 0.01 μm to 1.0 μm from the viewpoint of reducing the viscosity of the polymer polyol and the cut elongation of the urethane foam, and the lower limit is more preferably 0.8. 05 μm, particularly preferably 0.1 μm, and the upper limit is more preferably 0.7 μm, particularly preferably 0.5 μm.

The volume average particle diameter (R1) of the fine particles (P1) is suitably within the above particle diameter range so as to be a particle diameter suitable for obtaining polymer fine particles (JR) having a desired volume average particle diameter (R). Can be adjusted. For example, when polymer fine particles having a volume average particle diameter of 1 μm are desired, the volume average particle diameter (R1) of (P1) used is preferably 0.05 to 0.7 μm, particularly preferably 0.1 to 0. .5 μm. When it is desired to obtain polymer fine particles having a volume average particle size of 0.5 μm, (R1) of (P1) to be used is preferably 0.01 to 0.4 μm, particularly preferably 0.05 to 0.00. 3 μm. The volume average particle diameter (R) means the volume average particle diameter of the polymer fine particles (JR).

From the viewpoint of physical properties of the obtained polyurethane resin, the volume average particle diameter (R1) of (P1) and the volume average particle diameter (R) of the polymer fine particles (JR) are expressed by the following relational expressions (1) and (2). It is preferable to satisfy. Regarding the following relational expression (1), it is more preferable to satisfy the following relational expression (1 ′), and the following relational expression (1 ″) is particularly preferable. Regarding the following relational expression (2), it is more preferable to satisfy the following relational expression (2 ′), and the following relational expression (2 ″) is particularly preferable.

(R) ≦ (2.0) × (R1) × 3 √ [(V) / (Q)] (1)
(R) ≧ (R1) (2)
(R) ≦ (1.8) × (R1) × 3 √ [(V) / (Q)] (1 ')
(R) ≦ (1.6) × (R1) × 3 √ [(V) / (Q)] (1 '')
(R) ≧ (1.1) × (R1) (2 ′)
(R) ≧ (1.2) × (R1) (2 ″)

In the formula, (R) is the volume average particle diameter of (JR), R1 is the volume average particle diameter of (P1), V is the polymer fine particle content (vol%) of polymer polyol, Q is [[((P1) Weight × (specific gravity of (P1)] / [weight of polymer polyol × specific gravity of polymer polyol}].
The volume average particle diameter can be measured with a laser diffraction / scattered light particle size distribution analyzer (for example, LA-750, manufactured by Horiba, Ltd.).

Satisfying equation (2) indicates that (P1) having (R1) smaller than (R) is used, and in order to satisfy equation (2), (P1) satisfying this relationship is selected. do it.
Satisfying the formula (1) indicates that the part derived from the fine particles (P1) in the polymer fine particles (JR) has a specific ratio, that is, used in the polymerization step with respect to the amount of the fine particles (P1) used. It shows that the amount of the ethylenically unsaturated compound (E) used has a specific relationship. By satisfying this relationship, it is easy to obtain a polymer polyol having a sufficiently small particle size, and a polyurethane resin using the polymer polyol has no problem such as scorching and is excellent in mechanical strength such as cutting elongation.

In order to satisfy the formula (1), the ratio between the amount of the fine particles (P1) used and the amount of the ethylenically unsaturated compound (E) used may be adjusted. That is, when the formula (1) is not satisfied, it can be adjusted by increasing the amount of the fine particles (P1) used or decreasing the amount of the ethylenically unsaturated compound (E).

In the above, fine particle content (vol%) {where V1 is the fine particle (P1) content (vol%) of (B1), and Vn is the polymer fine particle content (vol%) of (B (n)). , (V) represents the polymer fine particle (JR) content (vol%) of the polymer polyol. } Is obtained by the following method.
<Method for measuring fine particle content (vol%)>
In a 50 ml centrifuge tube for centrifugation, about 5 g of the polymer polyol intermediate (B1, B (n)) or polymer polyol is precisely weighed to obtain the polymer polyol weight (W7). Add 50 g of methanol to dilute. Using a cooling centrifuge [model number: H-9R, manufactured by Kokusan Co., Ltd.], centrifuge at 18,000 rpm for 60 minutes at 20 ° C. The supernatant is removed using a glass pipette. The operation of adding 50 g of methanol to the residual sediment, diluting, and centrifuging in the same manner as above to remove the supernatant is repeated three more times. The residual sediment in the centrifuge tube is dried under reduced pressure at 2,666-3,999 Pa (20-30 torr) at 60 ° C. for 60 minutes, and the dried sediment is weighed to obtain (W8). The value calculated by the following equation is defined as the fine particle content (vol%).

Fine particle content (vol%) = (W8) × 100 / (W7) / (particle specific gravity) × (polymer polyol intermediate (B1, B (n)) or polymer polyol specific gravity)

The specific gravity of the particles can be determined by the Chemical Engineering Handbook [Revised 3rd Edition] (Basics II, p. 3 to 29) or the like, or by the method of JIS-Z8807. As for the specific gravity of the particles, the true specific gravity is used when there are no voids sealed inside such as porous particles or spherical particles. Further, when there is a sealed void such as a hollow particle, the bulk specific gravity is used.

The specific gravity of the polymer polyol intermediate (B1, B (n)) or polymer polyol can be determined by the method of JIS-B7525 “Specific gravity floating”.

When the fine particles (P1) are dispersed in the polyol (PL), a dispersing device can be used.
Generally, the dispersion apparatus is not particularly limited as long as it is an emulsifier or a disperser. For example, a batch type such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) or the like. Emulsifier, Ebara Milder (manufactured by Ebara Manufacturing Co., Ltd.), TK Fillmix, TK Pipeline Homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), thrasher, trigonal wet milling machine (Mitsui Continuous emulsifiers such as Miike Kako Co., Ltd., Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer (Nanomizer Co., Ltd.), APV Gaurin High-pressure emulsifiers (made by Gaurin), membrane emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), Vibro mixer (Chilling Industries Co., Ltd.) ) Vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

Fine particles (P1) are diluted with a diluting solvent (f) or a non-aqueous organic solvent (methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc .; ethyl acetate Ester, ester ether such as butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; ether such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as di-n-butyl ketone and cyclohexanone; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol; dimethylformamide and dimethyl It may be dispersed in advance in an amide such as acetoamide; a sulfoxide such as dimethyl sulfoxide; a heterocyclic compound such as N-methylpyrrolidone) and an aqueous solvent (water, methanol, ethanol, isopropanol, butanol, etc.).
The fine particles (P1) are preferably dispersed in the polyol (PL) in advance.
That is, in the step (1), when (E) is polymerized, it may be carried out in (PL) in the presence of (P1) and (c), and (P1) is dispersed in (PL) in advance. To the polymerization reactor, or the polyol (PL) and the fine particles (P1) (or a dispersion in which (P1) is previously dispersed in the diluting solvent (f)) may be separately charged into the polymerization reactor.

When the fine particles (P1) are dispersed in the polyol (PL) in advance, the fine particle content (% by weight) is 7 on the basis of the weight of (P1) and (PL) from the viewpoint of the physical properties of the polyurethane resin and the particle size of the polymer. Is preferably 30, more preferably 10 to 25, and particularly preferably 12 to 20.

When the fine particles (P1) are dispersed, the polyol (PL) is preferably a liquid. When the polyol (PL) is solid at room temperature, it may be dispersed in a liquid state at a high temperature above the melting point, or a solvent solution of (PL) may be used.
The viscosity of the polyol (PL) or its solvent solution when dispersing (P1) is usually 10 to 50,000 mPa · s (measured with a B-type viscometer), preferably 100 to 10, from the viewpoint of particle size uniformity. 000 mPa · s.
The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 5 to 98 ° C. When the viscosity of the dispersion is high, it is preferable to perform dispersion by adjusting the viscosity of the polyol (PL) or its solvent solution to the above-mentioned preferable range at a high temperature.
As the solvent used in the solvent solution of the polyol (PL), the same solvent as the diluting solvent (f) used at the time of polymerization can be used.

When the fine particles (P1) are dispersed in the polyol (PL), a known (Japanese Patent Laid-Open No. 2003-12706, etc.) emulsifier or a known (patent No. 2006-241198) used in the production of a polymer polyol is used. A dispersant (d) can also be used.

(P1) can also be obtained by polymerizing the ethylenically unsaturated compound (E) in the polyol (PL) in the presence of the radical polymerization initiator (c) and, if necessary, the dispersant (d). it can. As the polymerization method, a known polymerization method described later can be used.

(P1) is an ethylenically unsaturated compound (E) in the presence of a radical polymerization initiator (c) and, if necessary, a dispersant (d) in the polyol (PL) from the viewpoint of the storage stability of the polymer polyol. ) Is preferably obtained by polymerizing. Furthermore, it is preferable to use ACN and / or St as the ethylenically unsaturated compound (E) from the viewpoint of preventing scorch of the produced polyurethane resin.

The polymer polyol (I) of the present invention may contain an active hydrogen-containing compound (h) having an aromatic ring if necessary. In the production method described above, in step (1) and / or step (2), Polymerization may be carried out in the presence of (h). The Mn of the active hydrogen-containing compound (h) having an aromatic ring is 150 to 2,000, preferably 300 to 1,700, more preferably 500 to 500 from the viewpoint of the particle size of the polymer fine particles in the polymer polyol. 1,600. When Mn is less than 150 or exceeds 2,000, the volume average particle diameter of the polymer fine particles becomes large.

Here, the aromatic ring includes an aromatic ring in which only carbon forms a ring (benzene ring, naphthalene ring, etc.), an aromatic ring in which carbon and nitrogen form a ring (pyridine ring, etc.), and the like.

The content (% by weight) of the aromatic ring in (h) is preferably 4 to 90, preferably 8 to 70, more preferably 10 to 50, from the viewpoint of the volume average particle diameter of the polymer fine particles. The content of the aromatic ring means a value obtained by dividing the total atomic weight of the elements forming the ring structure by the molecular weight.

The active hydrogen in (h) is preferably 1 to 3 and more preferably 1 to 2 per molecule of (h) from the viewpoint of the volume average particle diameter of the polymer fine particles.
The active hydrogen equivalent of (h) (that is, the molecular weight per active hydrogen of (h)) is preferably from 100 to 2,000, more preferably from 150 to 1, from the viewpoint of the volume average particle diameter of the polymer fine particles. 700, and more preferably 250 to 1,600.

(H) includes aromatic ring-containing ether (h1), aromatic ring-containing ester (h2), aromatic ring-containing urethane (h3), and the like.
Examples of (h1) include compounds obtained by adding alkylene oxide to phenol such as bisphenol. Examples of phenol include monovalent phenols (cresol, naphthol, monostyrenated phenol, etc.), divalent phenols (catechol, resorcinol, bisphenol, etc.), trivalent or higher phenols (pyrogallol, etc.), and the like.
Examples of (h2) include compounds obtained by adding alkylene oxide to an aromatic ring-containing carboxylic acid such as phthalic acid. Examples of the aromatic ring-containing carboxylic acid include monovalent carboxylic acids (benzoic acid, salicylic acid, etc.), divalent carboxylic acids (phthalic acid, terephthalic acid, etc.), and trivalent or higher carboxylic acids (mellitic acid, etc.). .
Examples of (h3) include compounds obtained by polycondensation of an aromatic isocyanate such as TDI and a polyol. As aromatic isocyanate, monovalent isocyanate (phenyl isocyanate, etc.), divalent isocyanate (tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, etc.), trivalent or higher isocyanate (triphenylmethane triisocyanate) , Tris (isocyanate phenyl) thiophosphate, polymeric MDI, etc.).
Among these, (h1) is preferable from the viewpoint of the viscosity of (h).

In addition, (h) is an alkylene oxide adduct (h- 1) is preferred.
90 ≦ X ≦ 360 (3)
−0.012 × X + 14.0 ≦ S ≦ −0.012 × X + 16.0 (4)
In the formula, X represents the hydroxyl equivalent of the active hydrogen-containing compound (i), and S represents the SP value of the active hydrogen-containing compound (i).

95 ≦ X ≦ 340 (3 ′)
−0.012 × X + 14.1 ≦ S ≦ −0.012 × X + 15.8 (4 ′)
110 ≦ X ≦ 310 (3 ″)
−0.012 × X + 14.4 ≦ S ≦ −0.012 × X + 15.7 (4 ″)
The hydroxyl equivalent (X) of the active hydrogen-containing compound (i) preferably satisfies the formula (3) from the viewpoint of the viscosity of (i) and the particle size of the polymer fine particles in the polymer polyol, and more preferably the formula (3) ') Is satisfied, and particularly preferably, the expression (3'') is satisfied.
Further, from the viewpoint of the particle size of the polymer fine particles in the polymer polyol and the mechanical properties of the polyurethane resin, the relationship between the SP value of the active hydrogen-containing compound (i) and the hydroxyl group equivalent preferably satisfies the formula (4). Satisfies the formula (4 ′), and particularly preferably satisfies the formula (4 ″).

The hydroxyl equivalent (X) is a value that varies depending on the number of hydroxyl groups of the active hydrogen-containing compound (i) and the molecular weight of (i). The active hydrogen-containing compound (i) having the following may be selected.
In order for X and S to satisfy the above formula (4), the number of structures or functional groups in which the SP value other than the hydroxyl group of (i) is large and the number of structures or functional groups in which the SP value is small are adjusted. do it. For example, when S is smaller than the lower limit of the formula (4), the number of structures or functional groups having an SP value larger than 10 is increased, or the number of structures or functional groups having an SP value smaller than 10 is decreased. Therefore, it can be adjusted to satisfy the equation (4). When S is larger than the upper limit of the formula (4), the number of structures or functional groups having an SP value larger than 12 is reduced, or the number of structures or functional groups having an SP value smaller than 12 is decreased. It can be adjusted by increasing.

When the hydroxyl equivalent (X) satisfies the formula (3), it means that (i) contains an appropriate amount of a hydroxyl group, that is, a functional group to which an alkylene oxide can be added, and has a structure in which an alkylene oxide is added to this hydroxyl group. This means that (h-1) has an appropriate affinity for polyol (PL).
Further, when the SP value (S) of the hydroxyl group equivalent (X) and (i) satisfies the formula (4), depending on the amount of the hydroxyl group (i.e., the functional group to which alkylene oxide can be added) that (i) has, It means having an appropriate SP value. That is, (h) having a structure in which an alkylene oxide is added to (i) satisfying this relationship has an appropriate affinity for polymer fine particles (JR) according to the affinity with polyol (PL). It means having.
Therefore, (h-1) having a structure in which alkylene oxide is added to (i) satisfying these formulas (3) and (4) has an affinity for an appropriate polyol (PL) and an appropriate polymer fine particle ( JR) means that it has an appropriate balance and has a very good dispersibility of polymer fine particles.

From the viewpoint of particle diameter, the active hydrogen of (i) is preferably 1 to 3 per molecule of (i), more preferably 1 to 2.
In addition, the active hydrogen equivalent of (i) (that is, the molecular weight per active hydrogen of (i)) is preferably 60 to 500, more preferably 80 to 450, and still more preferably 100 to 500, from the viewpoint of particle diameter. 400.

Examples of (i) include bisphenol (i1), styrenated phenol (i2), and the like, and the same as phenol described above in (h1).
Examples of (i1) include bisphenol, and examples of (i2) include monostyrenated phenol and distyrenated phenol.
Among these, (i1) is preferable from the viewpoint of the viscosity of (h) and the particle diameter of the polymer fine particles in the polymer polyol.

Alkylene oxide is the same as described above, and preferred ones are also the same.

The alkylene oxide adduct (h-1) of the active hydrogen-containing compound (i) having at least one active hydrogen and having a hydroxyl group equivalent and an SP value satisfying the formulas (3) and (4) is specifically (H-1-1) bisphenol alkylene oxide adduct, (h-1-2) styrenated phenol alkylene oxide adduct, and the like.
Examples of (h-1-1) include compounds obtained by adding alkylene oxide to bisphenol, and examples of (h-1-2) include compounds obtained by adding alkylene oxide to monostyrenated phenol.
Among these, (h-1-1) is preferable from the viewpoint of the viscosity of (h) and the particle diameter of the polymer fine particles in the polymer polyol.

The content (% by weight) of (h) is preferably from 1 to 20, more preferably from the viewpoint of the volume average particle diameter of the polymer fine particles and the mechanical properties of the polyurethane resin, based on the weight of the polymer fine particles (JR). Is 1 to 15, then more preferably 1 to 10, particularly preferably 2 to 10, and most preferably 3 to 10.

The use amount (% by weight) of (h) in the dispersant (d) is preferably 5 to 100, more preferably 10 to 100, and particularly preferably 20 to 20 from the viewpoint of the particle size of the polymer fine particles in the polymer polyol. 100.

If necessary, the polymer polyol obtained by polymerization may be subjected to monomer removal / solvent removal treatment. As the demonomer / desolvent treatment, a known method (Japanese Patent Application Laid-Open No. 2004-002800) can be applied. From the viewpoint of the whiteness of the polyurethane resin, the residual monomer (ie, ethylenically unsaturated compound) and / or Alternatively, a method of stripping the diluting solvent (f) or a method of distilling under reduced pressure while continuously adding water (JP-B-62-36052, etc.) is preferable.

If necessary, a solvent and a flame retardant may be added to the polymer polyol (I) of the present invention. As the solvent, the same solvent as the diluting solvent (f) described above can be used, and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons are preferable from the viewpoint of the viscosity of the polymer polyol.
As the flame retardant, various flame retardants (such as those described in JP-A No. 2005-162791, etc., phosphate esters, halogenated phosphate esters, melamine, phosphazenes, etc.) can be used, from the viewpoint of the viscosity of the polymer polyol. A flame retardant having a low viscosity (100 mPa · s or less / 25 ° C.) is preferable, and among the halogenated phosphate esters, tris (chloroethyl) phosphate and tris (chloropropyl) phosphate are more preferable.
The amount (% by weight) of the solvent and the flame retardant used in the polymer polyol (I) is preferably 10 or less based on the total weight of the polymer fine particles (JR) and the polyol (PL). From the viewpoint of the flame retardancy of the resin and the mechanical properties of the resulting polyurethane resin, it is more preferably 0.01 to 5, more preferably 0.05 to 3, respectively.

The polymer polyol (I) of the present invention can be used as a polyol used for producing a polyurethane resin (polyurethane elastomer, polyurethane foam, etc.). That is, (I) or an isocyanate component (Is) comprising a polyol component (Po) containing (I) and a polyisocyanate [hereinafter, a composition comprising (Po) and (Is) is referred to as a polyurethane resin-forming composition. There is. ] Can be reacted by a known method {method described in JP-A-2004-263192 (corresponding US Patent Application: US2003 / 4217 A1)}, etc. to obtain a polyurethane resin.

As a polyol component (Po) used for producing a polyurethane resin, in addition to the polymer polyol (I) of the present invention, as a raw material for producing a polyurethane resin, a polyol is necessary as long as the effects of the present invention are not impaired. And known polymer polyols other than (I) may be used.
As the polyol, the above-described polyol (PL) or the like can be used, and as the known polymer polyol, JP 2005-162791 A, JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1) and the like are described. These polymer polyols can be used.
The amount (% by weight) of the polyol used can be appropriately adjusted from the viewpoint of the mechanical properties of the resulting polyurethane resin, but is preferably 1 to 1,000 based on the weight of the polymer polyol (I).
Based on the weight of (I), the used amount (% by weight) of a known polymer polyol other than the polymer polyol (I) is based on the mechanical properties of the polyurethane resin, the mechanical properties of the polyurethane resin, the eyes of the discharge ports of the strainer and the manufacturing apparatus. From the viewpoint of reducing clogging, 1 to 100 is preferable.

The amount (% by weight) of the polymer polyol (I) used in the polyol component (Po) is preferably 10 to 100, more preferably 15 to 90, from the viewpoint of the mechanical properties of the resulting polyurethane resin and the viscosity of the polyol component. Particularly preferred is 20 to 80, and most preferred is 25 to 70.

As the isocyanate component (Is), known polyisocyanates conventionally used in the production of polyurethane resins {JP 2005-162791 A, JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1)] Etc.} can be used.
Among these, from the viewpoint of mechanical properties of the polyurethane resin, 2,4- and 2,6-tolylene diisocyanate (TDI), a mixture of these isomers, crude TDI (residue when TDI is purified); 4 , 4'- and 2,4'-diphenylmethane diisocyanate (MDI), mixtures of these isomers, crude MDI (residue when MDI is purified); and urethane groups, carbodiimides derived from these polyisocyanates A modified polyisocyanate containing a group, allophanate group, urea group, burette group or isocyanurate group is preferred.

The NCO index [equivalent ratio of NCO group and active hydrogen atom (NCO group / active hydrogen atom) × 100] in the production of the polyurethane resin can be appropriately adjusted from the viewpoint of the mechanical properties of the polyurethane resin. Is more preferable, 85 to 120 is more preferable, and 95 to 115 is particularly preferable.

Various catalysts used in the urethanization reaction (JP 2005-162791 A, JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1), etc.) to promote the reaction in the production of the polyurethane resin Can be used. The amount (% by weight) of the catalyst used is preferably 10 or less, more preferably 0.001 to 5 based on the total weight of the polyurethane resin-forming composition.

In the production of polyurethane resin, various foaming agents {described in JP-A-2006-152188, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1), etc.} [water, HFC ( Hydrofluorocarbon), HCFC (hydrochlorofluorocarbon), methylene chloride, etc.] can be used to form a polyurethane foam. The amount (% by weight) of the foaming agent can be changed depending on the desired density of the polyurethane foam, and is not particularly limited, but is preferably 20 or less based on the total weight of the polyurethane resin-forming composition.
When producing a polyurethane foam, a foam stabilizer can be used if necessary. As the foam stabilizer, various foam stabilizers (as described in JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1), etc.) can be used, and in polyurethane foam From the viewpoint of uniformity of cell diameter, a silicone surfactant (for example, polysiloxane-polyoxyalkylene copolymer) is preferable.
The amount (% by weight) of the foam stabilizer used is preferably 5 or less, more preferably 0.01 to 2, based on the total weight of the polyurethane resin-forming composition.

In the production of the polyurethane resin, a flame retardant can be used if necessary. Various flame retardants {as described in JP 2005-162791 A, JP 2004-263192 A (corresponding US Patent Application: US 2003/4217 A1)}, for example, melamine, phosphate ester, halogenated Examples thereof include phosphate esters and phosphazenes.
The amount (% by weight) of the flame retardant used is preferably 30 or less, more preferably 0.01 to 10, based on the total weight of the polyurethane resin-forming composition.

In the production of the polyurethane resin, if necessary, it is selected from the group consisting of reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides, and fillers (including carbon black). At least one other additive can be used.

The polyurethane resin can be produced by various methods {methods described in JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1)}, and the one-shot method. And semi-prepolymer method and prepolymer method.
For the production of the polyurethane resin, a conventionally used production apparatus (such as a low-pressure or high-pressure machine) can be used. In the case of no solvent, an apparatus such as a kneader or an extruder can be used. Moreover, when manufacturing non-foaming or foaming polyurethane resin, a closed mold or an open mold can be used.
When the polymer polyol (I) of the present invention is used, clogging of a small opening of a production apparatus used for producing a polyurethane resin is reduced, maintenance is facilitated, and productivity can be improved. Particularly in a polyurethane foam foaming machine, clogging of the discharge head is extremely reduced and the productivity is remarkably improved.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
(1) Polyol Polyol (PL1-1): A polyol having a hydroxyl value of 56 and an internal EO unit content of 5.5%, in which glycerin is block-added in the order of PO-EO-PO. Terminal primary ratio = 2 mol%. [Product name "Sanniks (registered trademark) GP-3030", manufactured by Sanyo Chemical Industries, Ltd.]
Polyol (PL1-2): A polyol having a hydroxyl value of 32 and a terminal EO unit content of 14%, which is obtained by block addition of pentaerythritol in the order of PO-EO. Terminal primary conversion rate = 74 mol%. [Product name "Sanniks KC-757", manufactured by Sanyo Chemical Industries, Ltd.]
Polyol (PL1-3): A polyol having a hydroxyl value of 37.5 and a terminal EO unit content of 14%, added in the order of PO-EO to glycerin.
Polyol (PL1-4): Polyol added to pentaerythritol in the order of PO-EO, having a hydroxyl value of 37 and a terminal EO unit content of 17.5%.
Polyol (PL1-5): Polyol obtained by adding PO to bisphenol A and having a hydroxyl value of 216 and a terminal PO unit content of 56%. Terminal primary ratio = 1 mol%.
Polyol (PL1-6): Polyol obtained by adding PO to glycerol using a tris (pentafluorophenyl) borane catalyst and having a hydroxyl value of 56 and an internal EO unit content of 0%. Terminal primary ratio = 70 mol%.
Polyol (PL1-7): A polyol having a hydroxyl value of 33.7 and a terminal EO unit content of 14%, which is block-added to glycerin in the order of PO-EO. Terminal primary ratio = 75 mol%.
Polyol (PL1-8): glycerin. Hydroxyl value = 1829.
Polyol (PL1-9): PO adduct of sorbitol. Hydroxyl value = 490.
(2) Radical polymerization initiator c-1: 1,1′-azobis (2-methylbutyronitrile) [trade name “V-59”, manufactured by Wako Pure Chemical Industries, Ltd.]
(3) Dispersant d-1: hydroxyl value = 20 obtained by jointing 0.14 mol of polyol (PL1-2) and 0.07 mol of 2-hydroxymethacrylate with 0.16 mol of TDI, number of unsaturated groups / nitrogen-containing Reactive dispersant having a base = 0.22 (see JP 2002-308920 A)
d-2: ACN-St copolymerized oligomer type non-reactive dispersant having a weight ratio of ACN to St of ACN: St = 70: 30 and Mn of 247,710 {content of this oligomer type dispersant is 10 It was used by mixing with polyol (PL1-7) so as to be in weight percent. Hydroxyl value of this mixture = 20.0}
(4) Polyisocyanate TDI-80: Trade name “Coronate T-80” (manufactured by Nippon Polyurethane Industry Co., Ltd.)
CE-729: TDI / polymeric MDI = 80/20 (weight ratio), trade name “CE-729” (manufactured by Nippon Polyurethane Industry Co., Ltd.)
(5) Catalyst Catalyst A: Trade name “DABCO” (triethylenediamine) [manufactured by Nippon Emulsifier Co., Ltd.]
Catalyst B: Trade name “Neostan U-28” (stannous octylate) [manufactured by Nitto Kasei Co., Ltd.]
Catalyst C: Trade name “TEDAL-33” (triethylenediamine / dipropylene glycol = 33% / 67% solution) [manufactured by Tosoh Corporation]
Catalyst D: Trade name “TOYOCAT ET” (bis-2-dimethylaminoethyl ether / dipropylene glycol = 70% / 30% solution) [manufactured by Tosoh Corporation]
(6) Foam stabilizer Product name “SRX-280A” (polyether siloxane polymer) [manufactured by Toray Dow Corning Silicone Co., Ltd.]
Product name “TEGSTAB B4900” (polyethersiloxane polymer) [Evonik Degussa Japan Co., Ltd.]
Product name “SZ-1346” (polyether siloxane polymer) [manufactured by Nippon Unicar Co., Ltd.]

The measurement and evaluation methods in the examples are as follows.
<Volume average particle diameter>
The obtained polymer polyol intermediate or polymer polyol is diluted with the polyol used for the production so that the laser light transmittance is 70 to 90%, and the volume average particle size ( μm).

Equipment: LA-750, manufactured by HORIBA, Ltd.
Measurement principle: Mie scattering theory Measurement range: 0.04 μm to 262 μm
Solution injection amount: He-Ne laser Measurement time: 20 seconds

<Volume average particle diameter>
According to the following formula.
Volume average particle diameter (μm) = Σ [q (J) × X (J)] / Σ [q (J)]
J: Particle size division number (1 to 85)
q (J): Frequency distribution value (%)
X (J): Particle size division number Jth particle size (μm)

<Measurement method of soluble polymer content (% by weight)> Reference <polymer fine particle content (% by weight)> Reference

<Viscosity of polymer polyol>
The polymer polyol is measured using a BL type viscometer [manufactured by Tokyo Keiki Co., Ltd.] under the conditions of No. 3 rotor, 12 rpm or 6 rpm, and 25 ° C.

Production Example 1 [Production of Polymer Polyol Intermediate (H-1)]
A four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dripping pump, a pressure reducing device, a Dimroth condenser, a nitrogen inlet and an outlet, was charged with polyols (PL1-1), (PL1-5), a dispersant (d- 1) and xylene were added in the number of parts shown in the initial charge of Table 1, and the temperature was raised to 130 ° C. with stirring. Subsequently, a monomer containing a polyol (PL1-1), a dispersant (d-1), ACN, St, divinylbenzene, a radical polymerization initiator (c-1) and xylene previously mixed in the number of parts shown in the monomer liquid of Table 1 The mixed solution (Z1) was continuously dropped at a rate of 25 parts / minute using a dropping pump, and after completion of the dropping, the mixture was further polymerized at 130 ° C. for 30 minutes. Further, the mixture was cooled to 25 ° C. to obtain a polymer polyol intermediate (H-1). The volume average particle diameter and polymer fine particle content (% by weight) of (H-1) were measured and shown in Table 1.

Production Examples 2 to 6 [Production of polymer polyol intermediates (H-2) to (H-6)]
In Production Example 1, polymer polyol intermediates (H-2) to (H-6) were obtained in the same manner as in Production Example 1, except that the initial charge and monomer solution mixed in the number of parts shown in Table 1 were used. The volume average particle diameter and polymer fine particle content (% by weight) of (H-2) to (H-6) were measured and shown in Table 1.

Production Example 7 [Production of Strength Improvement Agent b-1]
In a stainless steel autoclave of a stirrer and a temperature controller, 1 mol of glycerin PO adduct (Sannix GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1500, hydroxyl value 112.0), 6 mol of phthalic anhydride and an alkali catalyst Half esterification was performed by charging 0.020 mol of (N-ethylmorpholine) and reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, PO6 mol was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of the aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-1). The measured values of (b-1) are as follows. Hydroxyl value (mgKOH / g) = 61.5.

Production Example 8 [Production of Strength Improvement Agent b-2]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1500, hydroxyl value 112.0), 6 mol of phthalic anhydride and an alkali catalyst (N— Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 6 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of the aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-2). The measured values of (b-2) are as follows. Hydroxyl value (mgKOH / g) = 63.5.

Production Example 9 [Production of Strength Improvement Agent b-3]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox GP-3000 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 3000, hydroxyl value 56.0), 3 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-3). The measured values of (b-3) are as follows. Hydroxyl value (mgKOH / g) = 47.1.

Production Example 10 [Production of Strength Improvement Agent b-4]
In an autoclave similar to Production Example 7, 1 mol of glycerin PO adduct (Sanix GL-3000NS; Mn: 3000, hydroxyl value 56.0, manufactured by Sanyo Chemical Industries, Ltd.), 3 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-4). The measured values of (b-4) are as follows. Hydroxyl value (mgKOH / g) = 47.1.

Production Example 11 [Production of Strength Improvement Agent b-5]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (a-1), 3 mol of phthalic anhydride and 0.020 mol of alkali catalyst (N-ethylmorpholine) were charged, and 0.20 MPa in a nitrogen atmosphere. The reaction was carried out at 120 ± 10 ° C. for 1 hour for half esterification. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-5). The measured values of (b-5) are as follows. Hydroxyl value (mgKOH / g) = 47.1.

Production Example 12 [Production of Strength Improvement Agent b-6]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox KC-725 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 5000, hydroxyl value 34.0), 3 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of the aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-6). The measured values of (b-6) are as follows. Hydroxyl value (mgKOH / g) = 30.2.

Production Example 13 [Production of Strength Improvement Agent b-7]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox FA-921NS; Mn: 6000, hydroxyl value 28.0) manufactured by Sanyo Chemical Industries, Ltd., 3 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-7). The measured values of (b-7) are as follows. Hydroxyl value (mgKOH / g) = 25.6.

Production Example 14 [Production of Strength Improvement Agent b-8]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanix FA-921NS; Mn: 6000, hydroxyl value 28.0) manufactured by Sanyo Chemical Industries, Ltd., 9 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 9 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-8). The measured values of (b-8) are as follows. Hydroxyl value (mgKOH / g) = 21.8.

Production Example 15 [Production of Strength Improvement Agent b-9]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1500, hydroxyl value 112.0), 6 mol of phthalic anhydride and an alkali catalyst (N— Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 6 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After cooling to room temperature, charging 1 mol of trimellitic anhydride and esterifying at 0.20 MPa and 120 ± 10 ° C. for 1 hour, 2 mol of EO is 120 ± 10 ° C. and the pressure is 0.5 MPa or less. While being controlled, the solution was dropped over 2 hours and then aged at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-9). The measured values of (b-9) are as follows. Hydroxyl value (mgKOH / g) = 74.4.

Production Example 16 [Production of Strength Improvement Agent b-10]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1500, hydroxyl value 112.0), 6 mol of phthalic anhydride and an alkali catalyst (N— Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 6 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After cooling to room temperature, charging with 3 mol of trimellitic anhydride and esterifying at 0.20 MPa and 120 ± 10 ° C. for 1 hour, 6 mol of EO is 120 ± 10 ° C. and the pressure is 0.5 MPa or less. While being controlled, the solution was dropped over 2 hours and then aged at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-10). The measured values of (b-10) are as follows. Hydroxyl value (mgKOH / g) = 94.1.

Production Example 17 [Production of Strength Improvement Agent b-11]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (a-1), 3 mol of phthalic anhydride and 0.020 mol of alkali catalyst (N-ethylmorpholine) were charged, and 0.20 MPa in a nitrogen atmosphere. The reaction was carried out at 120 ± 10 ° C. for 1 hour for half esterification. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. Cool to room temperature, charge 1 mol of trimellitic anhydride, esterify at 0.20 MPa, 120 ± 10 ° C. for 1 hour, then 5 mol of EO at 120 ± 10 ° C., pressure 0.5 MPa or less The solution was dropped over 2 hours under control, and then aged at 120 ± 10 ° C. for 1 hour. After completion of the aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (b-11). The measured values of (b-11) are as follows. Hydroxyl value (mgKOH / g) = 58.2.

Production Example 18 [Production of Strength Improvement Agent b-12]
In the same autoclave as in Production Example 7, 1 mol of ethylene glycol, 2 mol of trimellitic anhydride, 2.2 mol of triethylamine as a catalyst, and 2 mol of THF (tetrahydrofuran) as a solvent were charged at 80 ± 10 ° C. in a nitrogen atmosphere. Half-esterification was performed for a time. Thereafter, 4 mol of EO was dropped as an R1 constituent raw material at 80 ± 10 ° C. and 0.5 MPa over 1 hour, followed by aging for 1 hour. After completion of aging, the catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a strength improver (b-12). The measured values of (b-1) are as follows. Hydroxyl value (mgKOH / g) = 371.5.

Production Example 19 [Production of Strength Improvement Agent b-13]
In the same autoclave as in Production Example 7, 1 mol of polyethylene glycol (PEG-200 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 200, hydroxyl value 560), 1 mol of trimellitic anhydride, and N-ethylmorpholine 0.02 as a catalyst 2 mol of THF was added as a solvent and a solvent, and half esterification was performed at 80 ± 10 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 2 mol of EO as the R1 constituent raw material was added dropwise over 2 hours while controlling to 80 ± 10 ° C. and 0.5 MPa or less, and aged for 3 hours. After aging, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver (b-2). The measured values of (b-13) are as follows. Hydroxyl value (mgKOH / g) = 350.6.

Production Example 20 [Production of Strength Improvement Agent b-14]
A strength improver b-3 was obtained in the same manner as in Production Example 19 except that 2 mol of trimellitic anhydride and 4 mol of EO were used instead of 1 mol of trimellitic anhydride and 2 mol of EO. The measured values of (b-14) are as follows. Hydroxyl value (mgKOH / g) = 295.3.

Production Example 21 [Production of Strength Improvement Agent b-15]
A strength improver b-4 was obtained in the same manner as in Production Example 19 except that pyromellitic anhydride was used instead of trimellitic anhydride and 6 mol of EO was used instead of 4 mol of EO. The measured values of (b-15) are as follows. Hydroxyl value (mgKOH / g) = 374.0.

Production Example 22 [Production of Strength Improvement Agent b-16]
The strength improver b-5 was prepared in the same manner as in Production Example 19 except that propylene glycol POEO adduct (PL-910; Mn: 900, hydroxyl value 124) manufactured by Sanyo Chemical Industries, Ltd. was used instead of polyethylene glycol. Obtained. The measured values of (b-16) are as follows. Hydroxyl value (mgKOH / g) = 152.8.

Production Example 23 [Production of Strength Improvement Agent b-17]
1 mole of polytetramethylene glycol (PTMG-1000 manufactured by Mitsubishi Chemical Corporation; Mn: 1000, hydroxyl value 112) is added to a reactor equipped with a stirrer, temperature controller, pressure controller, cooler, trap, and liquid circulation pump. Then, 2 mol of trimellitic anhydride, 0.02 mol of N-ethylmorpholine as a catalyst, and 5 mol of toluene as a solvent were charged, and half esterification was performed at 80 ± 10 ° C. and 0.1 MPa for 2 hours in a nitrogen atmosphere. Thereafter, 4 mol of benzyl chloride was added as an R1 constituent raw material and reacted for 6 hours while controlling to 95 ± 5 ° C. and 0.06 MPa. During the reaction, volatile toluene and water were condensed with a cooler, and toluene separated by the trap was returned to the reactor again. After the reaction, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver b-17. The measured values of (b-17) are as follows. Hydroxyl value (mgKOH / g) = 0.

Production Example 24 [Production of Strength Improvement Agent b-18]
Instead of polytetramethylene glycol, 1 mol of polyethylene glycol (PEG-200 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 200, hydroxyl value 560), 1 mol of trimellitic anhydride, 0.02 N-ethylmorpholine as a catalyst A strength improver b-5 was obtained in the same manner as in Production Example 23 except that the molar amount was used. The measured values of (b-18) are as follows. Hydroxyl value (mgKOH / g) = 98.4.

Production Example 25 [Production of Strength Improvement Agent b-19]
The same autoclave as in Production Example 7 was charged with 2 mol of PEG-200, 1 mol of pyromellitic anhydride, 2.2 mol of triethylamine as a catalyst, and 2 mol of THF as a solvent, and half ester at 80 ± 10 ° C. for 2 hours in a nitrogen atmosphere. Made. Thereafter, 2 moles of ethylene bromide was added as an R1 constituent raw material and reacted at 80 ± 10 ° C. for 6 hours. After the reaction, the precipitated salt was filtered off, the organic layer was washed with water, and the target product was extracted and separated with toluene. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver b-19. The measured values of (b-19) are as follows. Hydroxyl value (mgKOH / g) = 332.9.

Production Example 26 [Production of Strength Improvement Agent b-20]
A strength improver b-20 was obtained in the same manner as in Production Example 25 except that ethylene bromide was changed to benzyl chloride. The measured values of (b-20) are as follows. Hydroxyl value (mgKOH / g) = 70.3.

Production Example 27 [Production of Strength Improvement Agent b-21]
A strength improver b-21 was obtained in the same manner as in Production Example 25 except that ethylene bromide was changed to phenyl chloride. The measured values of (b-21) are as follows. Hydroxyl value (mgKOH / g) = 72.9.

Production Example 28 [Production of Strength Improvement Agent b-22]
Similar to Production Example 23 except that polytetramethylene glycol was changed to PEG-200, 1 mol of trimellitic anhydride instead of 2 mol of trimellitic anhydride, and 2 mol of PP-200 instead of 4 mol of benzyl chloride. Operation was performed to obtain a strength improver b-23. The measured values of (b-23) are as follows. Hydroxyl value (mgKOH / g) = 224.3.

Production Example 29 [Production of Strength Improvement Agent b-23]
PEG-200 instead of polytetramethylene glycol, 1 mol of trimellitic anhydride instead of 2 mol of trimellitic anhydride, and 2 mol of benzylamine instead of 4 mol of benzyl chloride Operation was performed to obtain a strength improver b-23. The measured values of (b-23) are as follows. Hydroxyl value (mgKOH / g) = 98.4.

Production Example 30 [Production of Strength Improvement Agent b-24]
The same procedure as in Production Example 23, except that PEG-200 was substituted for polytetramethylene glycol, 1 mol of trimellitic anhydride was substituted for 2 mol of trimellitic anhydride, and 2 mol of diphenylamine was substituted for 4 mol of benzyl chloride. To obtain a strength improver b-24. The measured values of (b-24) are as follows. Hydroxyl value (mgKOH / g) = 80.8

Production Example 31 [Production of Strength Improvement Agent b-25]
PEG-200 instead of polytetramethylene glycol, 1 mol of trimellitic anhydride instead of 2 mol of trimellitic anhydride, and benzylthiol instead of 2 mol of benzyl chloride changed to 2 mol. Operation was performed to obtain a strength improver b-25. The measured values of (b-25) are as follows. Hydroxyl value (mgKOH / g) = 92.9.

Production Example 32 [Production of Strength Improvement Agent b-26]
Manufactured except PEG-200 instead of polytetramethylene glycol, 1 mole of trimellitic anhydride instead of 2 moles of trimellitic anhydride, 1 mole of ethylene glycol and 1 mole of benzylamine instead of 4 moles of benzyl chloride The same operation as in Example 23 was performed to obtain a strength improver b-26. The measured values of (b-26) are as follows. Hydroxyl value (mgKOH / g) = 221.3.

Production Example 33 [Production of Strength Improvement Agent b-27]
Production examples except that PEG-200 was substituted for polytetramethylene glycol, 1 mol of trimellitic anhydride was substituted for 2 mol of trimellitic anhydride, 1 mol of benzine alcohol and 1 mol of benzylamine were substituted for 4 mol of benzyl chloride In the same manner as in Example 23, a strength improver b-27 was obtained. The measured values of (b-27) are as follows. Hydroxyl value (mgKOH / g) = 98.2.

Production Example 34 [Production of Strength Improvement Agent b-28]
PEG-200 instead of polytetramethylene glycol, 1 mol of trimellitic anhydride instead of 2 mol of trimellitic anhydride, 1 mol of PEG-200 instead of 1 mol of benzyl chloride and 1 mol of benzylamine instead of 4 mol of benzyl chloride The same operation as in Production Example 23 was performed to obtain strength improver b-28. The measured values of (b-28) are as follows. Hydroxyl value (mgKOH / g) = 169.7.

Production Example 35 [Production of Strength Improvement Agent m-1]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox GP-3000 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 3000, hydroxyl value 56.0), 1 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 1 mol of PO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, and then aged at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (m-1). The measured values of (m-1) are as follows. Hydroxyl value (mgKOH / g) = 52.7.

Production Example 36 [Production of Strength Improvement Agent m-2]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 1500, hydroxyl value 112.0), 9 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 9 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After cooling to room temperature, charging with 3 mol of trimellitic anhydride and esterifying at 0.20 MPa and 120 ± 10 ° C. for 1 hour, 6 mol of EO is 120 ± 10 ° C. and the pressure is 0.5 MPa or less. While being controlled, the solution was dropped over 2 hours and then aged at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (m-2). The measured values of (m-2) are as follows. Hydroxyl value (mgKOH / g) = 80.3.

Production Example 37 [Production of Strength Improvement Agent m-3]
In the same autoclave as in Production Example 7, 1 mol of glycerin PO adduct (Sanyox FA-921 manufactured by Sanyo Chemical Industries, Ltd .; Mn: 6000, hydroxyl value 28.0), 1 mol of phthalic anhydride and an alkali catalyst (N- Ethylmorpholine) (0.020 mol) was charged, and half esterification was performed by reacting at 0.20 MPa at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 1 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (m-3). The measured values of (m-3) are as follows. Hydroxyl value (mgKOH / g) = 27.2.

The measurement method of the hydroxyl value of the manufactured strength improver and these units are shown below.
Hydroxyl value: Conforms to JIS K1557, unit is mgKOH / g

The analysis results of the strength improvers of Production Examples 7 to 37 are shown in Table 2.

In Table 2, the hydroxyl equivalent is defined by the following mathematical formula (5). Specifically, the hydroxyl value x is measured and determined by 56100 / hydroxyl value x.
(Hydroxyl equivalent) = (Number average molecular weight) / (Average number of hydroxyl groups) (5)

Example 1 [Production of polymer polyol (I-1)]
[First step] Two tanks of a continuous polymerization apparatus (SUS pressure-resistant reaction vessel connected with a liquid feed line and an overflow line) are prepared, and the first overflow line is connected to the inlet of the second polymerization tank in series. Deploy. An initial charge liquid in which polyol (PL1-1), polyol (PL1-6), polyol (b-2), and xylene were mixed in the parts shown in Table 3 in advance in the first tank and the second polymerization tank respectively. L-1) 2,000 parts were charged and the temperature was raised to 130 ° C. Polymer polyol intermediate (H-1), (PL1-1), (PL1-5), dispersant (d-1), ACN, St, allyl alcohol PO 2.2 mol adduct, divinylbenzene, radical polymerization initiator The raw material mixture (G1-1) in which (c-1) and xylene were mixed in the number of parts shown in Table 3 was line-blended using a static mixer, and then the first tank at the liquid feeding speed in the first tank shown in Table 3 Was continuously fed to the polymerization tank and overflowed from the polymerization tank to obtain a polymer polyol intermediate (IB1-1). Overflowing from the first polymerization tank (IB1-1) was continuously fed to the second polymerization tank at the first tank feeding speed shown in Table 3.
[Second Step] From the first tank, overflow (IB1-1), polyol (PL1-1), polyol (PL1-6), polyol (b- 2) A raw material mixture (G1-2) obtained by mixing ACN, St, radical polymerization initiator (c-1) and xylene in the number of parts shown in Table 3 was line-blended using a static mixer, and then shown in Table 3. The liquid was continuously fed to the second polymerization tank at the second liquid feeding speed, and the reaction liquid overflowed from the polymerization tank was stocked in a SUS receiving tank, and the polymer polyol intermediate (IB1- 2) was obtained. (IB1-2) was added with 2% of unreacted monomer and xylene while adding over-steam (amount of water contained in the steam was 4% by weight with respect to the polymer polyol over 2 hours) from another port. , 666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure to obtain a polymer polyol intermediate (IB1-3).
[Dilution step] Polyol (PL1-1) and polyols (b-1) to (b-16) are mixed in the parts shown in Table 3 to (IB1-3) to obtain polymer polyol (I-1). It was. (I-1) was evaluated by the measurement and evaluation methods described above. The results are shown in Table 5.

Examples 2 to 26 [Production of polymer polyols (I-2) to (I-26)]
In Example 1, the polymer polyol (I--) was used in the same manner as in Example 1 except that in the first step, the second step, and the dilution step, the initial charge and the raw material mixture shown in Tables 3 and 4 were used. 2) to (I-26) were obtained. (I-2) to (I-26) were measured and evaluated in the same manner as in Example 1. The results are shown in Tables 5 and 6.

Comparative Example 1 [Production of polymer polyol (R-1)]
A continuous polymerization apparatus (SUS pressure-resistant reaction vessel connected with a liquid feed line and an overflow line) was prepared, and an initial charge liquid (L-1) in which polyol (PL1-1) and xylene were previously mixed in the number of parts shown in Table 4 was prepared. 2,000 parts were charged and the temperature was raised to 130 ° C. Polyol (PL1-1), dispersant (d-1), ACN, St, allyl alcohol PO 2.2 mol adduct, divinylbenzene, radical polymerization initiator (c-1) and xylene are mixed in the parts shown in Table 4. The raw material mixture liquid (G1-1) was line-blended using a static mixer and then continuously fed to the polymerization tank at the liquid feed speed shown in Table 2 to overflow from the polymerization tank and polymer polyol intermediate (RB1- 1) was obtained. (RB1-1) is added with super-steam (amount of water contained in the vapor is 4% by weight with respect to the polymer polyol over 2 hours) from another port while adding unreacted monomer and xylene. , 666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure to obtain a polymer polyol intermediate (RB2-2).
[Dilution Step] Polyol (b-1) was mixed with (RB2-2) in the number of parts shown in Table 4 to obtain polymer polyol (R-1). (R-1) was evaluated by the measurement and evaluation methods described above. The results are shown in Table 6.
(R-1) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 6.

Comparative Example 2 [Production of polymer polyol (R-2)]
[First step] Two tanks of a continuous polymerization apparatus (SUS pressure-resistant reaction vessel connected with a liquid feed line and an overflow line) are prepared, and the first overflow line is connected to the inlet of the second polymerization tank in series. Deploy. Each of the first and second polymerization tanks was charged with 2,000 parts of an initial charge liquid (L-1) in which polyol (PL1-1) and xylene were previously mixed in the number of parts shown in Table 4, and the temperature was 130 ° C. The temperature was raised to. Polyol (PL1-1), dispersant (d-1), ACN, St, allyl alcohol PO 2.2 mol adduct, divinylbenzene, radical polymerization initiator (c-1) and xylene are mixed in the parts shown in Table 4. The raw material mixture (G1-3) was line blended using a static mixer, then continuously fed to the first polymerization tank at the first tank feeding speed shown in Table 4, and overflowed from the polymerization tank. To obtain a polymer polyol intermediate (RB2-1). Overflow from the first polymerization tank (RB2-1) was continuously fed to the second polymerization tank at the first tank feeding speed shown in Table 4.
[Second Step] (IB2-1) and polyol (PL1-1), ACN, St, radical polymerization initiator (c-) overflowed from the first tank to the first liquid feeding speed shown in Table 4 1) and the raw material mixture (G1-4) in which xylene was mixed in the number of parts shown in Table 4 were line-blended using a static mixer, and then the second tank was fed at the speed of the second tank shown in Table 4. The solution was continuously fed to the polymerization tank, and the reaction liquid overflowed from the polymerization tank was stocked in a SUS receiving tank to obtain a polymer polyol intermediate (RB2-3). (RB2-3) was added with super-steam (amount of water contained in the steam was 4% by weight with respect to the polymer polyol over 2 hours) from another port while adding unreacted monomer and xylene. , 666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure to obtain a polymer polyol intermediate (RB2-4).
[Dilution step] Polyol (PL1-1), polyol (b-1), polyol (m-1), and polyol (m-2) in (RB2-4) are mixed in the number of parts shown in Table 4 to obtain a polymer. A polyol (R-2) was obtained. (R-2) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 6.

Comparative Examples 3 to 5 [Production of polymer polyols (R-3) to (R-5)]
In Comparative Example 2, in the same manner as in Comparative Example 2, except that the initial charge and the raw material mixture shown in Table 4 were used in the first step, the second step and the dilution step, the polymer polyol (R-3) to (R-5) was obtained. (R-3) to (R-5) were measured and evaluated in the same manner as in Comparative Example 2. The results are shown in Table 6.

From the results of Tables 5 and 6, the following was found.
(1) In all of Examples 1 to 26, the value of soluble polymer content / polymer fine particle content is smaller than in Comparative Examples 1 and 2.
(2) In all of Examples 1 to 26, the volume average particle size of the polymer fine particles is smaller than that of Comparative Examples 1 and 2.

Example 27 [Production of polymer polyol (I-27)]
[First step] Two tanks of a continuous polymerization apparatus (SUS pressure-resistant reaction vessel connected with a liquid feed line and an overflow line) are prepared, and the first overflow line is connected to the inlet of the second polymerization tank in series. Deploy. An initial charge liquid (L) in which polyol (PL1-3), polyol (PL1-4), polyol (b-2), and xylene were previously mixed in the first and second polymerization tanks in the number of parts shown in Table 7, respectively. -2) 2,000 parts were charged and the temperature was raised to 130 ° C. Raw material mixture (G1-5) in which polyol (PL1-3), polyol (PL1-4), (d-2), ACN, St and radical polymerization initiator (c-1) were mixed in the number of parts shown in Table 7 Was line-blended using a static mixer, and then continuously fed to the first polymerization tank at the liquid feeding speed of the first tank shown in Table 7, and overflowed from the polymerization tank to cause a polymer polyol intermediate (IB27-1). ) Overflowing from the first polymerization tank (IB27-1) was continuously fed to the second polymerization tank at the first tank feeding speed shown in Table 7.
[Second Step] From the first tank, overflow (IB1-27), polyol (PL1-3), polyol (PL1-4), polyol (b- 2) The raw material mixture (G1-6) in which ACN, St and radical polymerization initiator (c-1) were mixed in the number of parts shown in Table 7 was line-blended using a static mixer, and then the two tanks shown in Table 7 The polymer polyol intermediate (IB27-2) was continuously fed to the second polymerization tank at the rate of the first liquid feed, and the reaction liquid overflowed from the polymerization tank was stocked in a SUS receiving tank. Got. Unreacted monomer while adding pervapor (from the polymer polyol intermediate (IB27-2), the amount of water contained in the steam is 4% by weight with respect to the polymer polyol over a period of 2 hours) from another port. And xylene were stripped at 2,666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure to obtain a polymer polyol intermediate (IB27-3).
[Dilution Step] Table 7 shows polyols (b-2), (b-6) to (b-8), and (b-16) to (b-29) with respect to the polymer polyol intermediate (IB27-3). Polymer polyol (I-27) was obtained by mixing in the indicated number of parts. (I-27) was evaluated by the measurement and evaluation methods described above. The results are shown in Table 9.

Examples 28 to 47 [Production of polymer polyols (I-28) to (I-47)]
In Example 27, the polymer polyol (I-- 28) to (I-47) were obtained. (I-28) to (I-47) were measured and evaluated in the same manner as in Example 1. The results are shown in Table 9.

Comparative Example 6 [Production of polymer polyol (R-6)]
[First step] Two tanks of a continuous polymerization apparatus (SUS pressure-resistant reaction vessel connected with a liquid feed line and an overflow line) are prepared, and the first overflow line is connected to the inlet of the second polymerization tank in series. Deploy. 2,000 parts of initial charge liquid (L-1) in which polyol (PL1-3), polyol (PL1-4) and xylene were mixed in advance in the number of parts shown in Table 8 respectively in the first and second polymerization tanks. Was charged and the temperature was raised to 130 ° C. Raw material mixture (G1-7) in which polyol (PL1-3), polyol (PL1-4), (d-2), ACN, St and radical polymerization initiator (c-1) were mixed in the number of parts shown in Table 8 Was line-blended using a static mixer, and then continuously fed to the first polymerization tank at the liquid feeding speed of the first tank shown in Table 8, and overflowed from the polymerization tank to cause the polymer polyol intermediate (RB6-1). ) The polymer polyol intermediate (RB6-1) overflowed from the first polymerization tank was continuously fed to the second polymerization tank at the first tank feeding speed shown in Table 8.
[Second Step] The polymer polyol intermediate (RB6-1) and polyol (PL1-3), polyol (PL1-4) overflowed from the first tank to the liquid feeding speed of the first tank shown in Table 8; A raw material mixture (G1-8) in which ACN, St and radical polymerization initiator (c-1) were mixed in the number of parts shown in Table 8 was line blended using a static mixer, and then the second tank shown in Table 8 was fed. The polymer polyol intermediate (RB6-2) was obtained by continuously sending the solution to the second polymerization tank at a liquid speed and stocking the reaction liquid overflowed from the polymerization tank in a SUS receiving tank. . (RB6-2) was added with 2% of unreacted monomer and xylene while adding over-steam (amount of water contained in the steam was 4% by weight with respect to the polymer polyol over 2 hours) from another port. , 666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure to obtain a polymer polyol intermediate (RB6-3).
[Dilution step] Polyol (PL1-3) and (PL1-4) and polyol (m-3) were mixed in the parts shown in Table 8 with respect to polymer polyol intermediate (RB6-3), and polymer polyol (R- 6) was obtained. The polymer polyol (R-6) was measured and evaluated in the same manner as in Example 27. The results are shown in Table 9.

Comparative Example 7 [Production of polymer polyol (R-7)]
In Comparative Example 6, the polymer polyol (R-7) was prepared in the same manner as in Comparative Example 6 except that the initial charge and the raw material mixture shown in Table 8 were used in the first step, the second step, and the dilution step. Obtained. (R-7) was measured and evaluated in the same manner as in Comparative Example 6. The results are shown in Table 9.

From the results in Table 9, the following was found.
(1) In all of Examples 27 to 47, the value of soluble polymer content / polymer fine particle content is smaller than that of Comparative Example 6.
(2) In all of Examples 27 to 47, the volume average particle diameter of the polymer fine particles is smaller than that of Comparative Example 6.

Examples 48 to 73, Comparative Examples 8 to 12 [Production of polyurethane foam]
The polymer polyols (I-1) to (I-26) obtained in Examples 1 to 26 and the comparative polymer polyols (R-1) to (R-5) obtained in Comparative Examples 1 to 5 were used. Polyurethane foams were produced by the foaming formulation shown below at the blending ratios shown in Table 10 and Table 11. The physical properties of these foams were evaluated by the following methods. The results are shown in Table 10 and Table 11.
<Foaming prescription>
[1] The temperature of each polymer polyol and polyisocyanate was adjusted to 25 ± 2 ° C.
[2] Polymer polyol, foam stabilizer, water, catalyst are charged in a stainless steel beaker and stirred and mixed at 25 ° C ± 2 ° C. (Mixing conditions: 2,000 rpm × 8 seconds).
[3] After the stirring was stopped, the contents of the beaker mixed in a wooden box (25 ° C. ± 2 ° C.) of 25 × 25 × 10 cm were added and foamed to obtain a polyurethane foam.

<Methods for evaluating foam physical properties of Examples 48 to 73 and Comparative Examples 8 to 12 in Table 10 and Table 11>
(1) Density (kg / m ³ ): compliant with JIS K6400-1997 [Item 5] (2) 25% ILD (hardness) (kgf / 314 cm ² ): compliant with JIS K6401-1997 (3) Tensile strength (kgf / Cm ² ): compliant with JIS K6301-1995 [item 3] (4) Tear strength (kgf / cm): compliant with JIS K6301-1995 [item 9] (5) Cut elongation (%): JIS K6301-1995 [Item 3] compliant (6) Compression set (%): JIS K6382-1995 [Item 5.5] compliant (7) Air permeability (ml / cm ² / s): JIS K6400-7-2004 [Item 4]

From the results of Table 10 and Table 11, the following was found.
(1) Compared with Examples 48 to 73, Comparative Examples 8 to 10 and 12 are inferior in 25% ILD, tensile strength, and tear strength.
(2) Compared with Examples 48 to 73, Comparative Examples 8 and 9 have inferior cutting elongation.
(3) Therefore, Examples 48 to 73 of the present invention have a satisfactory result in 25% ILD, tensile strength, and tear strength compared to Comparative Examples 8 to 10 and 12, and are excellent in mechanical properties. Is obtained.

In general, the physical properties of polyurethane foam indicate that 25% ILD, tensile strength, tear strength, cutting elongation and air permeability are better as the numerical value is larger, and compression set is smaller as the numerical value is smaller.

Examples 74 to 94, Comparative Examples 13 and 14 [Production of polyurethane foam]
The polymer polyols (I-27) to (I-47) obtained in Examples 27 to 47 and the polymer polyols (R-6) and (R-7) obtained in Comparative Examples 6 and 7 were used. 12, each raw material is stirred and mixed at 25 ± 2 ° C., the mold temperature is 60 ± 5 ° C., the mold size is 40 × 40 × 10 (H) cm, and the curing time is 6 minutes. A polyurethane foam was produced. The physical properties of these foams were evaluated by the following methods. The results are shown in Table 12.

<Methods for evaluating foam physical properties of Examples 74 to 94 and Comparative Examples 13 and 14 in Table 12>
(1) Density (kg / m ³ ): compliant with JIS K6400-1997 [Item 5] (2) 25% ILD (hardness) (kgf / 314 cm ² ): compliant with JIS K6401-1997 (3) Tensile strength (kgf / Cm ² ): compliant with JIS K6301-1995 [item 3] (4) Tear strength (kgf / cm): compliant with JIS K6301-1995 [item 9] (5) Cut elongation (%): JIS K6301-1995 [Item 3] compliant (6) Compression set (%): JIS K6382-1995 [Item 5.5] compliant

From the results in Table 12, the following was found.
(1) Compared with Examples 74 to 94, Comparative Examples 13 and 14 are inferior in 25% ILD, tensile strength, tear strength, and cut elongation.
(2) Therefore, in Examples 74 to 94 of the present invention, satisfactory results were obtained in terms of 25% ILD, tensile strength, tear strength, and cut elongation compared to Comparative Examples 13 and 14, and the mechanical properties were excellent. A polyurethane foam is obtained.

In general, the physical properties of polyurethane foam indicate that 25% ILD, tensile strength, tear strength, and elongation at break are better as the numerical value is larger, and compression set is smaller as the numerical value is smaller.

Since the polymer polyol of the present invention improves the mechanical properties of polyurethane, it can be used widely in a wide range of polyurethanes such as foams (soft, rigid, semi-rigid foams), elastomers, RIM molded products and the like. In particular, when used for the production of polyurethane foam, the physical properties of the polyurethane foam can be adjusted with good balance, which is preferable.
Polyurethanes formed from the polyurethane-forming composition of the present invention are used in a wide variety of applications. Particularly, they are suitably used as polyurethane foams for automobile interior parts, indoor furniture for furniture, and the like.

Claims

In a polymer polyol in which polymer fine particles (JR) containing an ethylenically unsaturated compound (E) as a structural unit are contained in a polyol (PL), (PL) contains the following strength improver (b). , (JR) polymer polyol (I) having a volume average particle diameter (R) of 0.1 to 1.5 μm.
Strength improver (b): at least one compound selected from the group consisting of an ester compound, a thioester compound, a phosphate ester compound and an amide compound, wherein a divalent or higher aromatic polyvalent carboxylic acid is an essential constituent Compound
The polymer polyol according to claim 1, wherein the strength improver (b) is a compound represented by the following general formula (I).

[In the general formula (I), R1 represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphate compound; a compound having two or more active hydrogen-containing functional groups in the molecule. These active hydrogen-containing compounds can be used either alone or in combination. That is, the plurality of R1s may be the same or different. Y represents a residue obtained by removing a carboxyl group from a trivalent or higher aromatic polycarboxylic acid. a is an integer satisfying 2 ≦ a ≦ the number of aromatic ring substituents−2. Z represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m. m represents an integer of 1 to 10. ]
The polymer polyol according to claim 1 or 2, wherein the content of the strength improver (b) is 10 to 100% by weight based on the weight of the polyol (PL).
4. The polymer polyol according to claim 1, wherein the volume average particle diameter (R) of the polymer fine particles (JR) is 0.1 to 0.9 μm.
The polymer polyol according to any one of claims 1 to 4, wherein the content of the polymer fine particles (JR) is 10 to 50% by weight based on the weight of the polymer polyol (I).
6. The ratio (soluble polymer content / polymer fine particle content) between the soluble polymer content (% by weight) and the polymer fine particle content (% by weight) is 1/10 or less. The polymer polyol described.
In the method for producing a polyurethane by reacting a polyol component and an isocyanate component, the polyol component contains 10 to 100% by weight of the polymer polyol (I) according to any one of claims 1 to 6 based on the weight of the polyol component. A method for producing polyurethane.