JP4493633B2 - Method for producing polymer polyol - Google Patents

Description

  The present invention relates to a method for producing a polymer polyol. More specifically, the present invention relates to a method for producing a polymer polyol suitable as a raw material for polyurethane foam and polyurethane elastomer, and a method for producing a polyurethane resin using the same.

Polymer polyols are used as raw materials for polyurethane resins to improve the physical properties of polyurethane foam, such as increasing the compression hardness and improving durability, and polymerize ethylenically unsaturated monomers in the presence of a polymerization initiator in the polyol. Can be obtained. In recent years, polymer polyols having a small average particle size have been desired for the purpose of further improving mechanical properties such as cutting elongation. In order to reduce the particle size, there is a method (see Patent Document 1) in which the ratio of acrylonitrile used as a part of the ethylenically unsaturated monomer used is increased, which is preformed in the first step polymerization. A process is also described in which a seed dispersion composed of submicron particles is prepared and a monomer is added to the seed dispersion in the second step to obtain a desired polymer concentration. In addition, a method for obtaining particles using pre-formed submicron particles as nuclei is known (see Patent Document 2).
JP-A-6-172462 JP-A-9-309937

  However, when the polymer polyol obtained by the method of Patent Document 1 is used, scorching is likely to occur due to the high acrylonitrile ratio of the polymer in slab foam applications, and in the method of Patent Document 2, a small particle diameter is obtained. Because a large amount of a high-molecular-weight polyol called a bonded polyol, which is obtained by jointing a polyol with an isocyanate, is used in a polyol that becomes a polymerization field, the viscosity of the polymer polyol is high, and the cut elongation of the resulting polyurethane foam is insufficient. There was a problem.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by performing a plurality of stages of polymerization under specific conditions, and have reached the present invention. .
That is, the present invention is the following three inventions.
[1] A polymer polyol in the first step of polymerizing a monomer-containing mixed solution (A1) comprising a polyol (a), an ethylenically unsaturated monomer (d), a radical polymerization initiator (k), and a dispersant (e). Intermediate (B1) is obtained, then polyol (a), ethylenically unsaturated monomer (d), radical polymerization initiator (k), dispersant (e), and base polymer polyol (h1) [ie intermediate ( B1)] is a method for producing a polymer polyol in the second step of polymerizing the monomer-containing mixed liquid (A2), and (d) in (A1) and (A2) before the start of polymerization in each step The concentration (mass%) of the polymer is 7 to 25, the polymer content (mass%) in (h1) is 7 to 25, and the conversion ratio (mass%) of the polymer (d) in each step (d). ) Is 80 or more and (d) is polymerized. The conversion rate (mass%) from the beginning to the polymer (mass%) up to 80 is a conversion rate (mass% / min) of 8 or more, and the polymer content (mass%) in the resulting polymer polyol (I) is 30. It is -45, The manufacturing method of polymer polyol (I) characterized by the above-mentioned.
[2] Polymer polyol in the first step of polymerizing the monomer-containing mixed solution (A1) comprising the polyol (a), the ethylenically unsaturated monomer (d), the radical polymerization initiator (k), and the dispersant (e) Intermediate (B1) is obtained, then polyol (a), ethylenically unsaturated monomer (d), radical polymerization initiator (k), dispersant (e), and base polymer polyol (hi) [ie intermediate (Bi)] is polymerized to obtain a polymer polyol intermediate (Bi + 1), and (Bi + 1) is used as the base polymer polyol (hi + 1) in the next step. In the same manner, the step of polymerizing (d) is repeated n-1 times from i = 1 to i = n−1 (where i is an integer from 1 to n−1) to produce a polymer polyol. And the total number of repetitions n is 3 to 3. The concentration (mass%) of (d) in (A1) and (Ai + 1) before the start of polymerization in each step is 7 to 25, and the polymer content (mass%) in (hi) 7 to 50, and the polymer content (% by mass) in the resulting polymer polyol (I) is 30 to 65. A method for producing a polymer polyol (I)
[3] In a method for producing a polyurethane resin by reacting a polyol component and a polyisocyanate component in the presence of at least one selected from a catalyst, a foaming agent, and a foam stabilizer as necessary, at least a part of the polyol component A process for producing a polyurethane resin, characterized in that the polymer polyol (I) obtained by the production method of [1] or [2] above is used.

  According to the production method of the present invention, even when the content of acrylonitrile in the monomer is low, a polymer polyol having a sufficiently small particle size and a narrow particle size distribution can be obtained. Excellent strength. Furthermore, a low-viscosity polymer polyol can be obtained.

  The monomer-containing mixed solution (A) used in the production method of the present invention comprises a polyol (a), an ethylenically unsaturated monomer (d), a radical polymerization initiator (k), a dispersant (e), and a base polymer polyol ( h). However, the base polymer polyol (h) is not used in the monomer-containing mixed solution (A1) in the first step.

  In the present invention, as the polyol (a), a known polyol that is usually used for production of a polymer polyol can be used. For example, a compound having a structure in which an alkylene oxide is added to a compound (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.) containing at least two (preferably 2 to 8) active hydrogens ( a1) and mixtures thereof. Among these, a compound having a structure in which an alkylene oxide is added to a polyhydric alcohol is preferable.

  Examples of polyhydric alcohols 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, neopentyl glycol. And alicyclic diols such as cyclohexane diol and cycloalkylene glycol such as cyclohexane dimethanol, trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylol propane and trimethylol) Alkanetriols such as ethane and hexanetriol); 4 to 8 or more polyhydric alcohols having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, such as dipentaerythritol, alkane polyols and intramolecular or intermolecular dehydration product thereof or alkane triol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.

  Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone;

Examples of amines include ammonia; aliphatic amines, alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, isopropanolamine, and aminoethylethanolamine), and alkylamines having 1 to 20 carbon atoms (for example, n -Butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), polyalkylenepolyamines (dialkylenetriamine having 2 to 6 carbon atoms in the alkylene group) to hexaalkyleneheptamine For example, diethylenetriamine and triethylenetetramine).
C6-C20 aromatic mono- or polyamines (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, and diphenyletherdiamine); C4-C20 alicyclic Examples include amines (isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine); heterocyclic amines having 4 to 20 carbon atoms (for example, aminoethylpiperazine) and the like.

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

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

Specific examples of the polyol include those obtained by adding PO to the active hydrogen-containing compound and those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO), preferably EO in the following manner, Alternatively, an esterified product of these addition compounds and polycarboxylic acid or phosphoric acid can be used.
(1) Block added in the order of PO-AO (Chiped)
(2) Block added in the order of PO-AO-PO-AO (balanced)
(3) Blocks added in the order of AO-PO-AO (4) Blocks added in the order of PO-AO-PO (active secondary)
(5) Random adduct 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 equivalent of (a1) is preferably 200 to 4,000. More preferably, it is 400-3,000. It is also preferable to use two or more kinds of (a1) in combination so that the hydroxyl equivalent is within this range.

As the polyol (a), another polyol (a2) can be used together with the compound (a1) having a structure in which an alkylene oxide is added to the active hydrogen-containing compound. In this case, the use ratio (mass ratio) of (a1) / (a2) is preferably 100/0 to 80/20.
Examples of (a2) include polymer polyols such as polyester polyols and diene polyols, and mixtures thereof.

  Examples of the polyester polyol include the above-mentioned polyhydric alcohol and / or polyether polyol [ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Polyhydric alcohols or mixtures thereof with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane, and alkylene oxide low-molar (1 to 10 mol) adducts of these polyhydric alcohols], and the polycarboxylic acid Alternatively, condensation with an anhydride or an ester-forming derivative such as a lower alkyl (carbon number of alkyl group: 1 to 4) ester (for example, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.) Reactants, or A condensation reaction product of a hydric alcohol and / or a polyether polyol and the carboxylic acid anhydride and an alkylene oxide; an addition reaction product of an alkylene oxide (EO, PO, etc.) of the condensation reaction product; a polylactone polyol such as the polyhydric alcohol Can be obtained by ring-opening polymerization of a lactone (e.g., ε-caprolactone) using an initiator; polycarbonate polyol, for example, a reaction product of the polyhydric alcohol and alkylene carbonate; and the like.

Furthermore, diene polyols such as polybutadiene polyol and hydrogenated products thereof; hydroxyl group-containing vinyl polymers such as acrylic polyols; natural oil polyols such as castor oil; modified products of natural oil polyols, and the like.
These polyols (a2) usually have 2 to 8, preferably 3 to 8, hydroxyl groups and usually have a hydroxyl equivalent of 200 to 4,000, preferably 400 to 3,000.
The number average molecular weight of the polyol (a) (according to gel permeation chromatograph (GPC), the same applies to the following number average molecular weight unless otherwise specified) is usually 500 or more, preferably 500 to 20,000, particularly preferably 1. , 200 to 15,000, most preferably 2,000 to 9,000. When the number average molecular weight is 500 or more, it is preferable from the viewpoint of foaming property of the polyurethane foam, and when it is 20,000 or less, the viscosity becomes low and the handling property of the polymer polyol is preferable. The hydroxyl equivalent of (a) is preferably 200 to 4,000, more preferably 400 to 3,000.

Examples of the ethylenically unsaturated monomer (d) used in the monomer-containing mixed solution (A) in the present invention include an unsaturated nitrile (d1), an aromatic ring-containing monomer (d2), (meth) acrylic acid esters (d3), Examples thereof include polyoxyalkylene ether (d4) of an α-alkenyl group-containing compound, other ethylenically unsaturated monomer (d5), and a mixture of two or more thereof.
Examples of (d1) include acrylonitrile and methacrylonitrile.
Examples of (d2) include styrene, α-methylstyrene, hydroxystyrene, chlorostyrene, and the like.
Examples of (d3) include those composed only of C, H, and O atoms, and include methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meta ) 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 (Meth) acrylic acid alkyl esters (alkyl group having 1 to 24 carbon atoms); hydroxypolyoxyalkylene (alkylene group having 2 to 8 carbon atoms) mono (meth) acrylates and the like. In the present invention, (meth) acrylate means acrylate and / or methacrylate, and the same description method is used hereinafter. The same applies to (meth) acrylic acid, (meth) allyl and the like.
Examples of (d4) include alkylene oxide adducts of terminal unsaturated alcohols having 3 to 24 carbon atoms. Examples of terminal unsaturated alcohols include allyl alcohol, 2-buten-1-ol, and 3-buten-2-ol. , 3-buten-1-ol, 1-hexen-3-ol and the like. Preference is given to alkylene oxide adducts of allyl alcohol.
The number of oxyalkylene units in (d4) is usually 1-9, preferably 1-6, more preferably 1-3. As said alkylene oxide, the thing similar to what was illustrated as an alkylene oxide added to an active hydrogen containing compound in the term of the above-mentioned polyol (a) is mentioned. Preferably, PO and / or EO.
The number average molecular weight of (d4) is usually 110 to 490, the lower limit is preferably 112, more preferably 116, particularly preferably 170, most preferably 180, and the upper limit is preferably 480, more preferably. 450, particularly preferably 420, most preferably 300. When the number average molecular weight is 110 or more, the viscosity of the polymer polyol is low, which is preferable in terms of handleability, and the hardness of the polyurethane resin obtained therefrom is also good. When the number average molecular weight of (d4) is 490 or less, the hardness of the polyurethane resin obtained using the number average molecular weight is good.

  The number of α-alkenyl groups in (d4) may be at least one on average. The number is preferably 1 to 10, more preferably 1 to 2, particularly preferably 1. When the average number of α-alkenyl groups is less than 1, not only the viscosity of the polymer polyol that can be obtained by increasing the components soluble in the polyol increases, but also the physical properties of the polyurethane resin produced using these polyols are remarkably increased. Inferior.

Moreover, the solubility parameter SP value of (d4) is usually 9.5 to 13. The lower limit is preferably 9.8, and more preferably 10.0. The upper limit is preferably 12.5, more preferably 12.2. When the SP value of (d4) is 9.5 or more, the viscosity of the polymer polyol produced using these becomes low. Moreover, the compression hardness of the polyurethane resin obtained using a polymer polyol whose SP value is 13 or less is improved.
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. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

  Other ethylenically unsaturated monomers (d5) other than the above include (meth) acrylamide; vinyl group-containing carboxylic acids such as (meth) acrylic acid and derivatives thereof; aliphatic hydrocarbon monomers such as ethylene and propylene; Fluorine-containing vinyl monomers such as perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate; other nitrogen-containing vinyl monomers such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicon; cyclic such as norbornene, cyclopentadiene and norbornadiene Olefin compounds; and the like.

  Furthermore, in addition to these monofunctional monomers, a small amount of a bifunctional or higher polyfunctional monomer (d6) other than those described above (except for those corresponding to bifunctional or higher (d4)) is used in (d) to obtain a polymer. The dispersion stability of the polyol can be further improved. Examples of the polyfunctional monomer include divinylbenzene, ethylene di (meth) acrylate, polyalkylene oxide glycol di (meth) acrylate, pentaerythritol triallyl ether, trimethylolpropane tri (meth) acrylate, and International Publication WO01 / 009242. Examples thereof include unsaturated carboxylic acid and glycol esters having a number average molecular weight of 500 or more, and unsaturated alcohol and carboxylic acid esters.

In the present invention, the mass ratio of (d1), (d2), (d3), (d4), (d5) and (d6) in (d) is not particularly limited, and according to the production method of the present invention, the monomer Regardless of the composition, a good polymer polyol (I) can be obtained, but can be appropriately changed according to the required physical properties of the polyurethane.
The content of the polyoxyalkylene ether (d4) of the α-alkenyl group-containing compound is preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of reducing the viscosity of the polymer polyol (I). In view of physical properties (such as tensile strength) of the urethane resin obtained, the upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.
From the viewpoint of scorch resistance, the content of unsaturated nitrile (d1) (particularly acrylonitrile) is preferably 70% by mass or less, more preferably 15 to 60% by mass.
In addition, the content of the aromatic ring-containing monomer (d2) (particularly styrene) is preferably 98% by mass or less, more preferably 20 to 90% by mass, from the viewpoint of reducing the particle size of the polymer particles in (I). Especially preferably, it is 35-80 mass%.
The content of the monomer other than these in (d) is preferably 0 to 50% by mass, more preferably 0 to 20% by mass in (d3). (D5) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass. (D6) is preferably 0.01 to 0.7% by mass, more preferably 0.05 to 0.4% by mass.

  Next, as the radical polymerization initiator (k), one that generates a free radical and initiates polymerization can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4) -Trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and 1,1'-azobis (1-acetoxy- Azo compounds such as 1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, benzoyl Over oxide, organic peroxides such as lauroyl peroxide and peracetic acid; such as persulfates and perborates inorganic peroxides, and the like. In addition, these can use 2 or more types together.

  The use amount of the radical polymerization initiator (k) in (A) is preferably 0.05 to 20%, more preferably 0.1 to 5%, and particularly preferably 0.00 based on the mass of (d). 2 to 1.5%. When the amount of (k) used is in the range of 0.05 to 20% by mass, the polymerization rate of (d) in the polymer polyol is sufficiently high and the molecular weight is also large. It is excellent in terms of obtaining compression hardness and cutting elongation.

The type of the dispersant (e) used in combination in the monomer-containing mixed solution (A) is not particularly limited, and a normal dispersant used in a polymer polyol can be used.
For example, [1] a macromer type dispersant obtained by reacting a polyol such as an ethylenically unsaturated group-containing modified polyether polyol (for example, JP-A-08-333508) with an ethylenically unsaturated compound; [2] a polyol Two or more polyol affinity segments with a solubility parameter difference of 1.0 or less are used as side chains, and a polymer affinity segment with a solubility parameter difference of 2.0 or less with a polymer from a vinyl monomer is a main chain. A graft type dispersant in which a polyol and an oligomer such as a graft polymer (for example, JP-A No. 05-059134) are combined; [3] At least a part of the hydroxyl group of the polyol is methylene dihalide and / or ethylenedi A modified polyol having a high molecular weight by reaction with a halide (for example, JP-A-07-196749) [4] a vinyl oligomer having a weight average molecular weight of 1000 to 30000, at least a part of which is soluble in the polyol, and this oligomer and the ethylenic unsaturated of [1] And an oligomer type dispersant such as a dispersant (for example, JP-A-09-77968) using a group-containing modified polyether polyol in combination.
Among these, the types [1] and [4] are preferable. In any case, the number average molecular weight is preferably 1,000 to 10,000.
Moreover, the usage-amount in the case of using these normal dispersing agents is based on the mass of (d), Preferably it is 50% or less, More preferably, it is 40% or less.

As the dispersant (e), in addition to these ordinary dispersants, the reactive dispersant (e ′) described in JP-A-2002-308920 described below can be used, and in the same manner as the preferred dispersant described above. preferable.
The reactive dispersant (e ′) comprises a substantially saturated polyol (p) and a monofunctional active hydrogen compound (q) having at least one polymerizable unsaturated group via a polyisocyanate (f). A nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4.
Here, “substantially saturated” means that the degree of unsaturation measured by the measuring method specified in JISK-1557 (1970) is 0.2 meq / g or less (preferably 0.08 meq / g or less). means.

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

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

The polymerizable unsaturated group (q) is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably 1 to 3, particularly preferably 1. 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.

Examples of monohydroxy substituted unsaturated hydrocarbons include alkenols having 3 to 6 carbon atoms such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, 1 -Hexen-3-ol and the like; and alkynol such as propargyl alcohol.
Examples of monoesters of an unsaturated monocarboxylic acid and a dihydric alcohol include, for example, unsaturated monocarboxylic acids having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, and the dihydric alcohol (ethylene Monoesters with 2 to 12 carbon dihydric alcohols such as glycol, propylene glycol, butylene glycol), and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like.

Examples of monoesters of unsaturated dihydric alcohols and monocarboxylic acids include monoesters of unsaturated dihydric alcohols having 3 to 8 carbon atoms and 2 to 12 monocarboxylic acids such as acetic acid monoester of butenediol. Is mentioned.
Examples of the phenol having an alkenyl side chain group include phenols having an alkenyl side chain group having 2 to 8 carbon atoms in the alkenyl group, such as oxystyrene and hydroxy α-methylstyrene.
Examples of the unsaturated polyether monool include adducts of 1 to 50 mol of alkylene oxide (2 to 8 carbon atoms) of the monohydroxy-substituted unsaturated hydrocarbon or the phenol having the alkenyl side group [for example, polyoxyethylene (degree of polymerization) 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 (2 to 4 carbon atoms) (meth) acrylate [aminoethyl (meth) acrylate, etc.], monoalkyl ( C1-C12) Aminoalkyl (C2-C4) (Meth) acrylate [monomethylaminoethyl-methacrylate, etc.]; As (q) having a carboxyl group, the unsaturated monocarboxylic acid; having an SH group ( Examples of q) include compounds corresponding to the unsaturated monohydroxy compound (OH is replaced with SH). Examples of (q) having two or more polymerizable unsaturated groups include poly (meth) allyl ethers of trihydric, tetrahydric, polyhydric, and 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.

Among these, preferred compounds are alkenols having 3 to 6 carbon atoms, monoesters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and dihydric alcohols having 2 to 12 carbon atoms, and phenols having alkenyl side chain groups. More preferably, it is monoester of (meth) acrylic acid and ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, particularly preferably 2-hydroxyethyl (meth) acrylate.
The molecular weight of (q) is not particularly limited, but is preferably 1000 or less, particularly 500 or less.

  The polyisocyanate (f) is a compound having at least two isocyanate groups. The aromatic polyisocyanate (f1), the aliphatic polyisocyanate (f2), the alicyclic polyisocyanate (f3), the araliphatic polyisocyanate ( f4), modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups or oxazolidone group-containing modified products) (f5), and mixtures of two or more thereof Is mentioned.

Examples of (f1) include 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the same as the following polyisocyanates). Is mentioned. 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) or a mixture thereof: diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] Phosgenates: polyallyl polyisocyanate (PAPI), etc.], naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.
Examples of (f2) include aliphatic diisocyanates having 2 to 18 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

Examples of (f3) include alicyclic diisocyanates having 4 to 16 carbon atoms. Specific examples include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate.
Examples of (f4) include araliphatic diisocyanates having 8 to 15 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Examples of (f5) include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
Among these, preferred are aromatic diisocyanates, and more preferred are 2,4- and / or 2,6-TDI.

The nitrogen-containing bond of the reactive dispersant (e ′) 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 an amino group In this case, a urea bond is mainly generated. 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 substantially saturated polyol (p) and the isocyanate group of the polyisocyanate (f), the active hydrogen-containing group of the unsaturated monofunctional active hydrogen compound (q) ( Some of them are caused by the reaction of f) with an isocyanate group.

(E ′) is the average value of the ratio of the number of unsaturated groups to nitrogen-containing bonds derived from the NCO group of (f) in one molecule, as determined by the following formula: K is 0.1 to 0.4 (P), (q) and (f) are reacted at a small ratio.
K = [number of moles of (q) × number of unsaturated groups of (q)] / [number of moles of (f) × number of NCO groups of (f)]
The value of K is more preferably 0.1 to 0.3, and particularly preferably 0.2 to 0.3. When the value of K is within the above range, the dispersion stability of the polymer polyol is particularly good.

  If necessary, a diluting solvent (c) may be added to the monomer-containing mixed solution (A). Examples of (c) include aromatic hydrocarbon solvents such as toluene and xylene; saturated aliphatic hydrocarbon solvents having 5 to 15 carbon atoms such as hexane, heptane, and normal decane; carbons such as octene, nonene, and decene. The unsaturated aliphatic hydrocarbon solvent having a number of 5 to 30 may be mentioned, and an aromatic hydrocarbon solvent is preferable. The amount of the diluting solvent (c) used is preferably 50% by mass or less, more preferably 1 to 40% by mass, based on the amount of (d) used. (C) used is preferably removed by vacuum stripping or the like after the polymerization reaction.

If necessary, (c) can be added to the polymer polyol (I) obtained by the method of the present invention to further reduce the viscosity. As (c) to be contained in (I), the unsaturated aliphatic hydrocarbon solvent; the aromatic hydrocarbon solvent; and a flame retardant having a low viscosity (100 mPa · s / 25 ° C. or less), such as tris (chloroethyl) ) Phosphate, tris (chloropropyl) phosphate; and the like.
The content of (c) in the obtained polymer polyol (I) is preferably 2% by mass or less, more preferably 1% by mass or less.

  Further, if necessary, the chain transfer agent (g) can be used in the monomer-containing mixed solution (A), and examples thereof include alkyl mercaptans such as dodecyl mercaptan and mercaptoethanol; The use amount of (g) is preferably 2% by mass or less, more preferably 0.1% by mass or less, based on the use amount of (d).

In the production method of the first invention, in the first step, a monomer-containing mixed solution comprising the polyol (a), the ethylenically unsaturated monomer (d), the radical polymerization initiator (k), and the dispersant (e). (A1) is polymerized to obtain a polymer polyol intermediate (B1). Next, in the second step, the obtained (B1) is used as the base polymer polyol (h1), and (h1), the polyol (a), the ethylenically unsaturated monomer (d), the radical polymerization initiator (k), And a monomer-containing mixed liquid (A2) composed of a dispersant (e) is polymerized to obtain a polymer polyol intermediate (B2), which is then subjected to monomer-removing and solvent-removing treatment as necessary to obtain a polymer polyol (I). .
In the second invention, a polymer polyol intermediate (B1) is obtained in the first step similar to the first invention, and then (B1) obtained in the second step is used as the base polymer polyol (h1). The polymer polyol intermediate (Bi) obtained in the i-th step (i is an integer from 1 to n-1, hereinafter the same) is used in the same manner as in the first invention. ) Repeated 1-5 times of the polymerization process using the base polymer polyol (hi) in the process (total number of repetitions n including the first process and the second process n = 3-7 times, where n is an integer), if necessary The same treatment is performed to obtain the polymer polyol (I).
In the production methods of the first and second inventions, the number of repetitions n of polymerization is usually 2 or more, preferably 3 or more from the viewpoint of maintaining a low monomer concentration, and from the viewpoint of productivity, the upper limit is usually 7 or more. Hereinafter, it is preferably 5 or less, more preferably 4 or less, and most preferably 3 or less. Within the above number of repetitions, the proportion of particles of 10 μm or more can be 2% by mass or less, which is preferable from the viewpoint of reducing the viscosity of the polymer polyol.

In the method for producing a polymer polyol of the present invention, at each repeated step, the base polymer polyol (h) obtained in the previous step is added to the polyol (a), the ethylenically unsaturated monomer (d), and radical polymerization is started. From the viewpoint of obtaining a polymer polyol having a small particle size and a narrow particle size distribution, it is preferable to prepare the monomer-containing mixed solution (A) to which the agent (k) and the dispersant (e) are added and to polymerize the mixture. . However, since (a) and a part of (e) are included in (h), (a) and (e) are not necessarily added. Such a case is also included in the present invention.
Further, the compositions of (a), (d), (k), and (e) used repeatedly for each step may be the same or different, but they are the same or substantially the same composition. Is preferred.

  In the method for producing a polymer polyol of the present invention, (k) is preliminarily mixed in the liquid mixture (A) and then heated to the polymerization occurrence temperature, and then (A) is heated to the polymerization occurrence temperature. , (K) may be added to start the polymerization. The latter is more economical and preferable because a smaller amount of radical polymerization initiator can be used.

  In the production method of the polymer polyol (I) of the first and second inventions, the concentration of the ethylenically unsaturated monomer (d) in the monomer-containing mixture (A) before the start of polymerization in each of the repeated steps is: From the viewpoint of productivity, the lower limit is usually 7% by mass or more, preferably 10% by mass or more, more preferably 11% by mass or more, and the viewpoint of reducing the average particle size of the polymer particles in the polymer polyol (I). Therefore, the upper limit is usually 25% by mass or less, preferably 24% by mass or less, and more preferably 22% by mass or less. When the concentration of (d) exceeds 25% by mass, the particle size of the polymer in the resulting polymer polyol increases. If it is less than 7% by mass, the content of the polyol-soluble oligomer component increases and the viscosity increases.

In the production method of the second invention, in each step after the second step, the concentration of the polymer of the ethylenically unsaturated monomer (d) in the base polymer polyol (h) is determined from the viewpoint of productivity. The lower limit is usually 7% by mass or more, preferably 10% by mass or more, more preferably 11% by mass or more. From the viewpoint of reducing the average particle size of the resin particles in the polymer polyol (I), the upper limit is usually 50% by mass. % Or less, preferably 48% by mass or less, more preferably 45% by mass or less. When the concentration of the polymer (d) exceeds 50% by mass, the particle size of the polymer in the polymer polyol obtained increases. If it is less than 7% by mass, the content of the polyol-soluble oligomer component increases and the viscosity increases.
In this 1st invention, the density | concentration of the polymer of (d) in the base polymer polyol (h1) used for a 2nd process is 7-25 mass% normally for the reason similar to the above, Preferably it is 10-25. It is 13 mass%, More preferably, it is 13-25 mass%.

In the method for producing a polymer polyol of the present invention, the polymerization may be performed in a continuous flow pipe or in a batch polymerization tank. The former is preferable from the viewpoint of productivity because the heat transfer area with respect to the contents is large and the heat of polymerization is easily removed.
In the present invention, the polymerization temperature (° C., hereinafter the same) is preferably 50 or more, more preferably 70 or more, particularly preferably 90 or more from the viewpoint of productivity, and from the viewpoint of preventing the decomposition of the polyol, the upper limit. Is preferably 200 or less, more preferably 180 or less, and particularly preferably 160 or less.

  In the method for producing a polymer polyol of the present invention, the lower limit of the conversion rate (% by mass) of the polymer (d) in each step is preferably 80% or more, more preferably 85, from the viewpoint of productivity. % Or more, particularly preferably 90% or more, and from the viewpoint of reducing the particle size, the upper limit is preferably 99.5% or less, more preferably 99% or less.

  In addition, the lower limit of the conversion rate from the start of polymerization (d) to the conversion rate of 80% (mass% / minute, hereinafter the same) for each step is preferably 8 or more, from the viewpoint of reducing the particle diameter. Preferably, it is 9 or more, particularly preferably 10 or more, and from the viewpoint of productivity [the amount of radical polymerization initiator (k) used, etc.], the upper limit is preferably 100 or less, more preferably 50 or less, particularly preferably 30 or less. It is.

  When the number of polymerization repetitions n is 2 (the first invention), in order to obtain a polymer polyol having a small particle size and a narrow particle size distribution in two stages, the conversion rate of (d) to the polymer Is 80% by mass or more, and the conversion rate from the start of polymerization (d) to the conversion rate of 80% by mass needs to be 8 or more. Each preferable range is the same as described above.

In the second invention, the polymer content of the obtained polymer polyol (I) is, from the viewpoint of the cut elongation and compression hardness of the polyurethane resin obtained from the polyurethane resin, for example, polyurethane foam, the lower limit is usually 30% by mass or more, The upper limit is usually 65% by mass or less and preferably 60% by mass or less from the viewpoint of handling of the monomer-containing mixed liquid (A).
In the first invention, from the same viewpoint, the polymer content of the polymer polyol (I) is usually 30 to 45% by mass, preferably 35 to 44% by mass.

Laser diffraction / scattering particle size distribution analyzer (LA-750; Horiba) of polymer particles of ethylenically unsaturated monomer (d) in polymer polyol (I) obtained by the method for producing polymer polyol of the present invention In the particle size distribution on a volume basis when the range of 0.020 to 2000 μm is divided into 85 by the Seisakusho, the same applies below), the content of particles of 10 μm or more contained in the polymer particles is the polyurethane resin obtained therefrom From the viewpoint of physical properties (such as tear strength), it is preferably 2% by volume or less, more preferably 1% by volume or less, and particularly preferably 0% by volume. (All particle size distributions described below are based on volume.)
The polymer particles have a particle diameter substantially in the range of 0.020 to 2000 μm. Here, “substantially” means that 98% by mass or more, preferably 100% by mass has a particle diameter in this range.

  In the present invention, in the particle size distribution obtained by dividing the range of 0.020 to 2000 μm by 85 using a laser diffraction / scattering type particle size distribution measuring device of the polymer particles in (I) obtained, the volume reference of the polymer particles The arithmetic standard deviation according to is preferably 0.6 or less, more preferably 0.56 or less, and particularly preferably 0.4 or less. When the arithmetic standard deviation is 0.6 or less, the mechanical strength of the resulting polyurethane resin, particularly the cutting elongation and tear strength, are improved.

Further, in the particle size distribution when the range of 0.020 to 2000 μm is divided into 85 by a laser diffraction / scattering type particle size distribution measuring device, the arithmetic operation of the polymer particles of (d) in (I) obtained in the present invention is performed. When the average particle size is [R] (μm), the mode is [P] (volume basis:%), and the difference between the maximum particle size and the minimum particle size is [Q] (μm), the polymer particles are: It is preferable that the particles satisfy the range of the following formula (1). More preferably, the particles satisfy the following formula (1 ′), particularly preferably the following formula (1 ″). When the polymer particles satisfy the formula (1), the elongation (cut elongation) of the polyurethane resin is good. Become.

[P] / [Q] ≧ 1.7 × [R] ^−0.93 (1)

[P] / [Q] ≧ 1.71 × [R] ^−0.75 (1 ′)

[P] / [Q] ≧ 2.0 × [R] ^-0.65 (1 ")

In addition, the arithmetic average particle diameter [R] of the polymer particles (d) is preferably in the range of 0.3 to 3.0 μm, the lower limit is more preferably 0.4 μm, and the upper limit is more preferably 2. 0.0 μm, particularly preferably 1.0 μm. When [R] is in the range of 0.3 to 3.0 μm, the viscosity of the polymer polyol (I) is low, handling becomes easy, and the resulting polyurethane resin has good compression hardness and mechanical strength. .

  In the polymer polyol (I) obtained by the production method of the present invention, the content of coarse polymer particles having a diameter of 100 μm or more produced in the polymerization process is preferably in the range of 1 to 20 ppm. The upper limit is more preferably 15 ppm, particularly preferably 10 ppm. When the coarse polymer particles are 20 ppm or less, the opening is not easily blocked when filtering with a wire mesh or a strainer, and thus the productivity is remarkably improved.

  The polymer polyol (I) obtained by the production method of the present invention is used as at least a part of a polyol component used when producing a polyurethane resin. That is, using (I) as at least part of the polyol component, the reaction is conducted in the usual manner in the presence of a polyisocyanate component and, if necessary, one or more commonly used additives such as a catalyst, a foaming agent, and a foam stabilizer. To obtain a polyurethane resin. In addition to (I), the polyol component may contain the polyol (a) as necessary.

As the polyisocyanate component, known organic polyisocyanates that have been conventionally used in the production of polyurethane resins can be used. Examples of such polyisocyanate include those exemplified as the polyisocyanate (f).
Preferred among these are 2,4- and 2,6-TDI, mixtures of these isomers, crude TDI; 4,4′- and 2,4′-MDI, mixtures of these isomers, crude MDI; and modified polyisocyanates containing urethane, carbodiimide, allophanate, urea, burette, or isocyanurate groups derived from these polyisocyanates.

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

In order to accelerate the reaction in the production of the polyurethane resin, a catalyst usually used in the polyurethane reaction [for example, amine-based catalyst (tertiary amine such as triethylenediamine, N-ethylmorpholine), tin-based catalyst (stannic octylate, Dibutyltin dilaurate and the like, and other metal catalysts (such as lead octylate) and the like] can be used. The amount of catalyst is usually 0.001 to 5% based on the mass of the reaction mixture.
In the present invention, in the production of the polyurethane resin, a foaming agent (for example, water, HFC, HCFC, methylene chloride, etc.) can be used to obtain a polyurethane foam. The amount of blowing agent used can vary depending on the desired density of the polyurethane foam.
In the production of the polyurethane foam of the present invention, a foam stabilizer can be used if necessary. Examples of the foam stabilizer include a silicone surfactant (for example, polysiloxane-polyoxyalkylene copolymer).
In the production of the polyurethane resin (including polyurethane foam) of the present invention, a flame retardant can be used as necessary. Examples of the flame retardant include melamines, phosphate esters, halogenated phosphate esters, and phosphazene derivatives.
Other additives that can be used in the production method of the present invention include, for example, reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides, carbon black and other fillers. These additives may be mentioned.

The production of the polyurethane resin can be performed by an ordinary method, and can be performed by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method.
For the production of the polyurethane resin, a production apparatus usually used can be used. In the case of no solvent, for example, an apparatus such as a kneader or an extruder can be used. Various non-foamed or foamed polyurethane resins can be produced in a closed mold or an open mold. Polyurethane is usually produced by mixing and reacting raw materials using a low-pressure or high-pressure machine. Furthermore, before and after the raw material mixing (particularly before the raw material mixing), the polyurethane resin can be produced by removing gases such as dissolved air in the raw material or air mixed during the mixing by a vacuum method.

  The polymer polyol (I) obtained by the production method of the present invention is particularly useful for the production of polyurethane foams such as flexible mold foams and slab foams. Moreover, it can be used suitably also for shaping | molding by RIM (reaction injection molding) method.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the following, parts and ratios indicate parts by mass and mass ratio, respectively, unless otherwise specified.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
(1) Polyol (a1)
Polyol (a1-1): A polyol having a hydroxyl value of 56 and an internal EO unit content of 9% added to glycerin in the order of PO-EO-PO.
Polyol (a1-2): Polyol added with pentaerythritol in the order of PO-EO and having a hydroxyl value of 32 and a terminal EO unit content of 14% (2) radical polymerization initiator (k)
k-1: 2,2′-azobis (2,4-dimethylvaleronitrile)
k-2: 1,1′-azobis (cyclohexane-1-carbonitrile)
(3) Dispersant (e)
e-1: hydroxyl value = 20 obtained by jointing 0.14 mol of polyol (a1-2) and 0.07 mol of 2-hydroxyethyl methacrylate with 0.16 mol of TDI, number of unsaturated groups / number of nitrogen-containing groups = 0. 22 reactive dispersant (see JP 2002-308920 A)
(4) Organic polyisocyanate TDI-80: “Coronate T-80” [manufactured by Nippon Polyurethane Industry Co., Ltd.]
(5) Catalyst Catalyst A: “Neostan U-28” (stannous octylate) [manufactured by Nitto Kasei Co., Ltd.]
Catalyst B: “DABCO” (triethylenediamine) [manufactured by Nippon Emulsifier Co., Ltd.]
(6) Foaming agent “SRX-280A” (polyether siloxane polymer) [manufactured by Toray Dow Corning Silicone Co., Ltd.]

<Example 1> Production of polymer polyol (I-1); (d) concentration 23.2%, number of repetitions 2 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol (a1 -1): 323.5 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO2.2 mol adduct (number average molecular weight 186): 7.4 parts, divinylbenzene: 0.32 parts, dispersed Agent (e-1): 10.6 parts and xylene: 34 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer-containing polyol intermediate (B1-1).
[Repeated Second Step] Next, (B1-1) is used as the base polymer polyol (h1-1), and (h1-1) is polyol (a1-1): 40.5 parts, acrylonitrile: 47.6. Part, styrene: 111 parts, allyl alcohol PO 2.2 mol adduct: 11.1 parts, divinylbenzene: 0.48 parts, dispersant (e-1): 15.8 parts, and xylene: 11.5 parts. The temperature was adjusted to 90 ° C. with stirring. The liquid which melt | dissolved (k-1): 0.95 part and (k-2): 0.48 part in 5.3 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached the maximum temperature of 160 ° C. in about 6.5 minutes. After reaching the maximum temperature, the mixture was aged for 10 minutes to obtain a polymer polyol intermediate (B2-1). The unreacted monomer and xylene are stripped from (B2-1) at 2666-3999 Pa (20-30 torr) under reduced pressure for 2 hours, the polymer content is 40%, the volume average particle size is 0.46 μm, and the viscosity is 2800 mPa · s ( 25 degreeC) polymer polyol (I-1) was obtained.

<Example 2> Production of polymer polyol (I-2); (d) concentration 21.5%, number of repetitions 3 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol ( a1-1): 363 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO2.2 mol adduct: 7.4 parts, divinylbenzene: 0.32 parts, dispersant (e-1): 10.6 parts and xylene: 34 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, the mixture was aged for 10 minutes to obtain a polymer polyol intermediate (B1-2).
[Repeated Second Step] Next, using (B1-2) as the base polymer polyol (h1-2), (h1-2), polyol (a1-1): 20 parts, acrylonitrile: 44 parts, styrene: 104 parts , Allyl alcohol PO 2.2 mol adduct: 10.4 parts, divinylbenzene: 0.44 parts, dispersant (e-1): 14.8 parts, and xylene: 11.5 parts. The temperature was adjusted to ° C. The liquid which melt | dissolved (k-1): 0.88 part and (k-2): 0.44 part in 5.3 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, the mixture was aged for 10 minutes to obtain a polymer polyol intermediate (B2-2).
[Repeated Third Step] Further, (B2-2) is used as the base polymer polyol (h2-2) to (h2-2), polyol (a1-1): 27.4 parts, acrylonitrile: 62 parts, styrene: 145 parts, allyl alcohol PO 2.2 mol adduct: 14.5 parts, divinylbenzene: 0.62 part, dispersant (e-1): 20.7 parts, xylene: 16.2 parts, with stirring, The temperature was adjusted to 90 ° C. A solution prepared by dissolving (k-1): 1.24 parts and (k-2): 0.62 parts in 7.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B3-2). The unreacted monomer and xylene are stripped from (B3-2) at 2666-3999 Pa (20-30 torr) for 2 hours under reduced pressure to give a polymer content of 50%, a volume average particle size of 0.54 μm, and a viscosity of 5200 mPa · s ( 25 degreeC) polymer polyol (I-2) was obtained.

Example 3 Production of Polymer Polyol (I-3): Concentration of (d) 11.3%, Number of Repeats 3 Times [First Step] A polyol (a1) was placed in a water-cooled jacket type 1.5 L pressure-resistant reaction vessel. -1): 800 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO2.2 mol adduct: 7.4 parts, divinylbenzene: 0.32 parts, dispersant (e-1): 10 .6 parts, xylene: 75 parts was added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 9 minutes and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B1-3).
[Repeated Second Step] Next, using (B1-3) as the base polymer polyol (h1-3), (h1-3), polyol (a1-1): 16 parts, acrylonitrile: 37 parts, styrene: 87 parts , Allyl alcohol PO 2.2 mol adduct: 8.7 parts, divinylbenzene: 0.37 parts, dispersant (e-1): 12.4 parts, xylene: 9.7 parts, and stirred at 90 ° C. The temperature was adjusted. The liquid which melt | dissolved (k-1): 0.75 part and (k-2): 0.37 part in 5.2 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 9 minutes, and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B2-3).
[Repeated third step] Furthermore, (B2-3) was used as the base polymer polyol (h2-3) to (h2-3), polyol (a1-1): 19.4 parts, acrylonitrile: 44 parts, styrene: 102 parts, allyl alcohol PO2.2 mol adduct: 10.2 parts, divinylbenzene: 0.44 parts, dispersant (e-1): 14.6 parts, xylene: 11.4 parts, with stirring, The temperature was adjusted to 90 ° C. The liquid which melt | dissolved (k-1): 0.88 part and (k-2): 0.44 part in 5.3 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 9 minutes, and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B3-3). The unreacted monomer and xylene were stripped from (B3-3) at 2666-3999 Pa (20-30 torr) under reduced pressure for 2 hours to give a polymer content of 30%, a volume average particle size of 0.38 μm, and a viscosity of 3800 mPa · s ( 25 degreeC) polymer polyol (I-3) was obtained.

<Example 4> Production of polymer polyol (I-4); (d) concentration 15.6%, number of repetitions 4 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol (a1 -1): 522 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO2.2 mol adduct: 7.4 parts, divinylbenzene: 0.32 parts, dispersant (e-1): 10 .6 parts, xylene: 51 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 140 ° C. in about 7 minutes, and aging at the same temperature for 10 minutes to obtain a polymer polyol intermediate (B1-4).
[Repeated Second Step] Next, using (B1-4) as the base polymer polyol (h1-4), (h1-4), polyol (a1-1): 18 parts, acrylonitrile: 40 parts, styrene: 94 parts , Allyl alcohol PO 2.2 mol adduct: 9.4 parts, divinylbenzene: 0.40 parts, dispersant (e-1): 13.4 parts, xylene: 10.5 parts, and stirred at 90 ° C. The temperature was adjusted. The liquid which melt | dissolved (k-1): 0.81 part and (k-2): 0.40 part in 4.8 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 140 ° C. in about 7 minutes, and aging at that temperature for 10 minutes to obtain a polymer polyol intermediate (B2-4).
[Repeated Third Step] Further, (B2-4) is used as the base polymer polyol (h2-4) to (h2-4), polyol (a1-1): 22.6 parts, acrylonitrile: 51 parts, styrene: 119 parts, allyl alcohol PO 2.2 mol adduct: 12.0 parts, divinylbenzene: 0.51 part, dispersant (e-1): 17.1 part, xylene: 13.4 parts The temperature was adjusted to ° C. The liquid which melt | dissolved (k-1): 1.03 part and (k-2): 0.51 part in 6.2 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 140 ° C. in about 7 minutes, and aging at that temperature for 10 minutes to obtain a polymer polyol intermediate (B3-4).
[Repeated Fourth Step] Further, (B3-4) is used as the base polymer polyol (h3-4) to (h3-4), polyol (a1-1): 28.8 parts, acrylonitrile: 65 parts, styrene: 152 parts, allyl alcohol PO 2.2 mol adduct: 15.3 parts, divinylbenzene: 0.65 part, dispersant (e-1): 21.8 parts, xylene: 17.1 parts, 90% with stirring The temperature was adjusted to ° C. The liquid which melt | dissolved (k-1): 1.31 part and (k-2): 0.65 part in 7.8 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 140 ° C. in about 7 minutes, and aging at that temperature for 10 minutes to obtain a polymer-containing polyol intermediate (B4-4). . The unreacted monomer and xylene were stripped from (B4-4) at 2666-3999 Pa (20-30 torr) under reduced pressure for 2 hours to give a polymer content of 50%, a volume average particle size of 0.56 μm, and a viscosity of 5200 mPa · s ( 25 degreeC) polymer polyol (I-4) was obtained.

<Example 5> Production of polymer polyol (I-5); (d) concentration 11.8%, number of repetitions 6 times [First step] In a water-cooled jacket type 3 L pressure-resistant reaction vessel, polyol (a1-1 ): 755 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO 2.2 mol adduct: 7.4 parts, divinylbenzene: 0.32 parts, dispersant (e-1): 10.6 Part, xylene: 75 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 8 minutes, and aging at that temperature for 10 minutes to obtain a polymer-containing polyol intermediate (B1-5). .
[Repeated Second Step] Next, (B1-5) is used as the base polymer polyol (h1-5) to (h1-5), polyol (a1-1): 17 parts, acrylonitrile: 37 parts, styrene: 88 parts Allyl alcohol PO 2.2 mol adduct: 8.8 parts, divinylbenzene: 0.38 part, dispersant (e-1): 12.5 parts, xylene: 9.8 parts, and stirred at 90 ° C. Adjusted. The liquid which melt | dissolved (k-1): 0.75 part and (k-2): 0.38 part in 4.5 parts of xylene was mixed here, and superposition | polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 8 minutes, and aging at the same temperature for 10 minutes to obtain a polymer polyol intermediate (B2-5).
[Repeated Third Step] Further, (B2-5) is used as the base polymer polyol (h2-5) to (h2-5), polyol (a1-1): 19.7 parts, acrylonitrile: 45 parts, styrene: 104 parts, allyl alcohol PO 2.2 mol adduct: 10.4 parts, divinylbenzene: 0.45 parts, dispersant (e-1): 14.9 parts, xylene: 11.6 parts The temperature was adjusted to ° C. The liquid which melt | dissolved (k-1): 1.03 part and (k-2): 0.51 part in 6.2 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 8 minutes, and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B3-5).
[Repeated Fourth Step] Further, (B3-5) is used as the base polymer polyol (h3-5) to (h3-5), polyol (a1-1): 23.4 parts, acrylonitrile: 53 parts, styrene: 124 parts, allyl alcohol PO 2.2 mol adduct: 12.4 parts, divinylbenzene: 0.53 parts, dispersant (e-1): 17.6 parts, xylene: 13.8 parts, 90% with stirring The temperature was adjusted to ° C. The liquid which melt | dissolved (k-1): 1.06 part and (k-2): 0.53 part in 6.4 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 140 ° C. in about 8 minutes and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B4-5).
[Repeated 5th Step] Furthermore, (B4-5) is used as the base polymer polyol (h4-5) to (h4-5), polyol (a1-1): 27.7 parts, acrylonitrile: 63 parts, styrene: 147 parts, allyl alcohol PO 2.2 mol adduct: 14.7 parts, divinylbenzene: 0.63 parts, dispersant (e-1): 20.9 parts, xylene: 16.4 parts The temperature was adjusted to ° C. A solution prepared by dissolving (k-1): 1.26 parts and (k-2): 0.63 parts in 7.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 8 minutes and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B5-5).
[Repeated Step 6] Further, (B5-5) is used as the base polymer polyol (h5-5) to (h5-5), polyol (a1-1): 32.9 parts, acrylonitrile: 75 parts, styrene: 174 parts, allyl alcohol PO 2.2 mol adduct: 17.4 parts, divinylbenzene: 0.75 parts, dispersant (e-1): 24.8 parts, xylene: 19.5 parts, and with stirring, 90 parts The temperature was adjusted to ° C. A solution prepared by dissolving (k-1): 1.49 parts and (k-2): 0.75 parts in 8.9 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly, reaching the maximum temperature of 125 ° C. in about 8 minutes, and aging for 10 minutes at the same temperature to obtain a polymer polyol intermediate (B6-5). The unreacted monomer and xylene are stripped from (B6-5) at 2666-3999 Pa (20-30 torr) for 2 hours under reduced pressure to give a polymer content of 50%, a volume average particle size of 0.52 μm, and a viscosity of 5000 mPa · s ( 25 degreeC) polymer polyol (I-5) was obtained.

<Example 6> Production of polymer polyol (I-6); (d) concentration 20.1%, number of repetitions 3 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol ( a1-1): 370 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, divinylbenzene: 0.32 parts, dispersant (e-1): 10.6 parts, and xylene: 34 parts and stirring The temperature was adjusted to 90 ° C. below. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B1-6).
[Repeated Second Step] Next, (B1-6) is used as the base polymer polyol (h1-6) to (h1-6), polyol (a1-1): 30 parts, acrylonitrile: 44 parts, styrene: 104 parts Divinylbenzene: 0.44 parts, Dispersant (e-1): 14.8 parts, and xylene: 11.5 parts, and the temperature was adjusted to 90 ° C. with stirring. The liquid which melt | dissolved (k-1): 0.88 part and (k-2): 0.44 part in 5.3 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B2-6).
[Repeated Third Step] Further, (B2-6) is used as the base polymer polyol (h2-6) to (h2-6), polyol (a1-1): 32 parts, acrylonitrile: 62 parts, styrene: 145 parts Divinylbenzene: 0.62 parts, Dispersant (e-1): 20.7 parts, Xylene: 16.2 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution prepared by dissolving (k-1): 1.24 parts and (k-2): 0.62 parts in 7.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B3-6). The unreacted monomer and xylene were stripped from (B3-6) at 2666-3999 Pa (20-30 torr) for 2 hours under reduced pressure to give a polymer content of 50%, a volume average particle size of 0.54 μm, and a viscosity of 5400 mPa · s ( 25 degreeC) polymer polyol (I-6) was obtained.

<Example 7> Production of polymer polyol (I-7); (d) concentration 24.0%, number of repetitions 3 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol ( a1-1): 340 parts, acrylonitrile: 53 parts, styrene: 53 parts, allyl alcohol PO2.2 mol adduct: 7.4 parts, divinylbenzene: 0.32 parts, and dispersant (e-1): 10 6 parts were added and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 4 minutes. After reaching the maximum temperature, it was aged for 10 minutes to obtain a polymer polyol intermediate (B1-7).
[Repeated Second Step] Next, (B1-7) is used as the base polymer polyol (h1-7) to (h1-7), polyol (a1-1): 40 parts, acrylonitrile: 78 parts, styrene: 78 parts Allyl alcohol PO 2.2 mol adduct: 10.9 parts, divinylbenzene: 0.47 parts, and dispersant (e-1): 15.5 parts were added, and the temperature was adjusted to 90 ° C. with stirring. The liquid which melt | dissolved (k-1): 0.93 part and (k-2): 0.46 part in 5.6 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 4 minutes. After reaching the maximum temperature, it was aged for 10 minutes to obtain a polymer polyol intermediate (B2-7).
[Repeated Third Step] Further, (B2-7) is used as the base polymer polyol (h2-7) to (h2-7), polyol (a1-1): 58.5 parts, acrylonitrile: 115 parts, styrene: 115 parts, allyl alcohol PO 2.2 mol adduct: 16.1 parts, divinylbenzene: 0.69 parts, and dispersant (e-1): 22.9 parts were added and the temperature was adjusted to 90 ° C. with stirring. . The liquid which melt | dissolved (k-1): 1.38 part and (k-2): 0.69 part in 8.2 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 4 minutes. After reaching the maximum temperature, the mixture was aged for 10 minutes to obtain a polymer polyol intermediate (B3-7). (B3-7), unreacted monomer and xylene were stripped under reduced pressure at 2666-3999 Pa (20-30 torr) for 2 hours to give a polymer content of 50%, a volume average particle size of 0.54 μm, and a viscosity of 5200 mPa · s ( 25 degreeC) polymer polyol (I-7) was obtained.

<Example 8> Production of polymer polyol (I-8); (d) concentration 21.5%, number of repetitions 3 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol ( a1-1): 363 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO6 mole adduct (number average molecular weight: 412): 7.4 parts, divinylbenzene: 0.32 parts, dispersant ( e-1): 10.6 parts and xylene: 34 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, it was aged for 10 minutes to obtain a polymer polyol intermediate (B1-8).
[Repeated Second Step] Next, (B1-8) is used as the base polymer polyol (h1-8) to (h1-8), polyol (a1-1): 20 parts, acrylonitrile: 44 parts, styrene: 104 parts , Allyl alcohol PO6 molar adduct: 10.4 parts, divinylbenzene: 0.44 parts, dispersant (e-1): 14.8 parts, and xylene: 11.5 parts, and stirred at 90 ° C. The temperature was adjusted. The liquid which melt | dissolved (k-1): 0.88 part and (k-2): 0.44 part in 5.3 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B2-8).
[Repeated Third Step] Further, (B2-8) is used as the base polymer polyol (h2-8) to (h2-8), polyol (a1-1): 27.4 parts, acrylonitrile: 62 parts, styrene: 145 parts, allyl alcohol PO6 molar adduct: 14.5 parts, divinylbenzene: 0.62 part, dispersant (e-1): 20.7 parts, xylene: 16.2 parts are added and stirred at 90 ° C. The temperature was adjusted. A solution prepared by dissolving (k-1): 1.24 parts and (k-2): 0.62 parts in 7.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, it was aged for 10 minutes to obtain a polymer polyol intermediate (B3-8). (B3-8), unreacted monomer and xylene were stripped under reduced pressure at 2666-3999 Pa (20-30 torr) for 2 hours to give a polymer content of 50%, a volume average particle size of 0.54 μm, and a viscosity of 4900 mPa · s ( 25 degreeC) polymer polyol (I-8) was obtained.

<Example 9> Production of polymer polyol (I-9); (d) concentration 20.9%, number of repetitions 3 times [First step] In a water-cooled jacket type 1.5 L pressure-resistant reaction vessel, polyol ( a1-1): 363 parts, acrylonitrile: 31.7 parts, styrene: 74 parts, allyl alcohol PO2.2 mol adduct: 3.2 parts, divinylbenzene: 0.32 parts, dispersant (e-1): 10.6 parts and xylene: 34 parts were added, and the temperature was adjusted to 90 ° C. with stirring. A solution obtained by dissolving radical polymerization initiator (k-1): 1.06 parts and (k-2): 0.32 parts in 5.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B1-9).
[Repeated Second Step] Next, using (B1-9) as the base polymer polyol (h1-9), (h1-9), polyol (a1-1): 20 parts, acrylonitrile: 44 parts, styrene: 104 parts , Allyl alcohol PO 2.2 mol adduct: 4.4 parts, divinylbenzene: 0.44 parts, dispersant (e-1): 14.8 parts, and xylene: 11.5 parts. The temperature was adjusted to ° C. The liquid which melt | dissolved (k-1): 0.88 part and (k-2): 0.44 part in 5.3 parts of xylene was mixed here, and polymerization was started. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, aging was performed for 10 minutes to obtain a polymer polyol intermediate (B2-9).
[Repeated Third Step] Further, (B2-9) is used as the base polymer polyol (h2-9) to (h2-9), polyol (a1-1): 27.4 parts, acrylonitrile: 62 parts, styrene: 145 parts, allyl alcohol PO 2.2 mol adduct: 6.2 parts, divinylbenzene: 0.62 parts, dispersant (e-1): 20.7 parts, xylene: 16.2 parts, and with stirring, The temperature was adjusted to 90 ° C. A solution prepared by dissolving (k-1): 1.24 parts and (k-2): 0.62 parts in 7.5 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization started rapidly within 1 minute, and reached a maximum temperature of 160 ° C. in about 6 minutes. After reaching the maximum temperature, it was aged for 10 minutes to obtain a polymer polyol intermediate (B3-9). (B3-9), unreacted monomer and xylene were stripped under reduced pressure at 2666-3999 Pa (20-30 torr) for 2 hours to give a polymer content of 50%, a volume average particle size of 0.54 μm, and a viscosity of 5400 mPa · s ( 25 degreeC) polymer polyol (I-9) was obtained.

<Comparative Example 1> Production of polymer polyol (R-1); (d) concentration 47.0%, no repetition In a water-cooled jacketed 1.5 L pressure-resistant reaction vessel, polyol (a1-1): 800 parts, Acrylonitrile: 150 parts, styrene: 350 parts, allyl alcohol PO 2.2 mol adduct: 35 parts, divinylbenzene: 1.5 parts, dispersant (e-1): 50 parts, xylene: 160 parts, and stirring The temperature was adjusted to 90 ° C. A solution prepared by dissolving 3.0 parts of radical polymerization initiator (k-1) and 1.5 parts of (k-2) in 18 parts of xylene was mixed here to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded quickly and aged for 10 minutes at a maximum temperature of 180 ° C. while cooling to obtain a polymer-containing polyol intermediate (C1-1). The unreacted monomer and xylene are stripped from (C1-1) at 2666-3999 Pa (20-30 torr) under reduced pressure for 2 hours to give a polymer content of 50%, a volume average particle size of 1.6 μm, and a viscosity of 10800 mPa · s ( 25 ° C.) comparative polymer polyol (R-1) was obtained.

<Comparative example 2>
Production of polymer polyol (R-2): concentration of (d) 30.0%, number of repetitions 2 times [first step] Polyol (a1-1): 395 in a water-cooled jacket type 1.5 L pressure-resistant reaction vessel Parts, acrylonitrile: 59 parts, styrene: 137 parts, allyl alcohol PO2.2 mol adduct: 13.7 parts, divinylbenzene: 0.59 parts, dispersant (e-1): 19.6 parts, xylene: 63 The temperature was adjusted to 90 ° C. with stirring. A solution prepared by dissolving radical polymerization initiator (k-1): 1.96 parts and (k-2): 0.59 parts in 10 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded quickly and aged for 10 minutes at a maximum temperature of 160 ° C. while cooling to obtain a polymer-containing polyol intermediate (C1-2).
[Repeated Second Step] Further, (C1-2) is used as the base polymer polyol (r1-2) to (r1-2), polyol (a1-1): 43 parts, acrylonitrile: 98 parts, styrene: 229 parts Allyl alcohol PO 2.2 mol adduct: 22.9 parts, divinylbenzene: 0.98 part, dispersant (e-1): 32.7 parts, xylene: 25.6 parts, and stirred at 90 ° C. The temperature was adjusted. A solution prepared by dissolving (k-1): 1.96 parts and (k-2): 0.98 parts in 12 parts of xylene was mixed to initiate polymerization. After the radical polymerization initiator solution was charged, the polymerization proceeded rapidly and aged for 10 minutes at a maximum temperature of 160 ° C. while cooling to obtain a polymer-containing polyol intermediate (C2-2). The unreacted monomer and xylene are stripped from (C2-2) at 2666-3999 Pa (20-30 torr) under reduced pressure for 2 hours to give a polymer content of 50%, a volume average particle size of 0.85 μm, and a viscosity of 6200 mPa · s ( 25 ° C.) comparative polymer polyol (R-2) was obtained.

The evaluation methods in Table 1 and Table 2 are as follows.
Measurement of the following particle diameter, arithmetic standard deviation, mode, etc. is carried out by diluting the obtained polymer polyol with the polyol used for it so that the transmittance of laser light is 70 to 90%. It measured with the particle size distribution measuring apparatus.
Apparatus: LA-750, manufactured by HORIBA, Ltd.
Measurement principle: Mie scattering theory Measurement range: 0.020 μm to 2000 μm
Light source: He-Ne laser (632.8 nm) 1 mW
Tungsten lamp 50W
Measurement time: 20 seconds Relative refractive index: 1.2 (relative solvent: polyol)

<Arithmetic mean particle size [R] and arithmetic standard deviation>
According to the following formula.
Arithmetic mean 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 J-th particle size (μm)

Arithmetic standard deviation = [[Σ [(X (J) −arithmetic mean particle diameter (μm)) ² × q (J) / 100]] ^1/2
<Maximum particle size, minimum particle size>
In the section in which the particle diameter is divided into 85, the maximum particle diameter and the minimum particle diameter are respectively shown among the particle diameters having a frequency (volume%) of 0.1 volume% or more. (Unit: μm)
<Mode [P]>
Abundance ratio (volume basis) of the particle diameter having the highest abundance ratio with respect to all particles in the section obtained by dividing the particle diameter into 85 (unit:%)

<Polymer content>
Polymer polyol is diluted with methanol so that polymer polyol / methanol = 1/3 (ratio). The polymer is separated by a cooling centrifuge (18000 rpm × 60 min. 20 ° C.), and the supernatant is removed. After repeating this three times, the polymer was dried under reduced pressure (60 ° C. × 1 hr), the mass was measured, and the ratio to the polymer polyol was determined.
<Viscosity>
Using a BL type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the measurement was performed under conditions of No. 3 rotor, 12 rpm, and 25 ° C.

<Conversion rate>
The conversion rate was calculated from the residual monomer content of each monomer with respect to the charged monomer amount, and obtained from the mass average. The residual monomer content was calculated from the area ratio with respect to the internal standard substance by gas chromatography. A specific analysis method is shown below using styrene as an example.
Conversion rate (% by mass)
= 100-100 × [(residual styrene content [%] / (styrene charge in raw material [%])]
Residual styrene content [%] = L / M x (factor for internal standard)
L = (peak area of residual styrene) / (mass of polymer polyol [g])
M = (peak area of internal standard substance) / (mass of internal standard substance [g])

The factor for the internal standard is the peak area of each monomer at the same mass divided by the peak area of the internal standard.
Gas chromatograph: GC-14B (manufactured by Shimadzu Corporation)
Column: inner diameter 4 mmφ, length 1.6 m, glass Column filler: polyethylene glycol 20M [manufactured by Shinwa Kako Co., Ltd.]
Internal reference material: Bromobenzene [manufactured by Nacalai Tesque, Inc.]
Diluent: Dipropylene glycol monomethyl ether grade 1 [Wako Pure
Yakuhin Co., Ltd.] (50% solution)
Injection temperature: 200 ° C
Column initial temperature: 110 ° C
Temperature increase rate: 5 ° C./min.
Column final temperature: 200 ° C
Sample injection volume: 1 μl

<Conversion speed>
The conversion rate (mass% / min) is obtained by dividing the conversion rate at a certain time from the start of polymerization by the above time from the start of polymerization. The conversion rate at a certain time from the start of the polymerization is measured by sampling the polymer polyol every hour from the start of the polymerization, and quickly adding a polymerization inhibitor (for example, hydroquinone) to deactivate the polymerization. This polymer polyol is analyzed by the above conversion rate measuring method. The time from the start of polymerization to a conversion rate of 80% is, for example, the time from the start of polymerization to a conversion rate of 75% and the time from the start of polymerization to a conversion rate of 85%. Plotting is performed by connecting two points with a straight line, and the time obtained at the conversion rate of 80% is shown.

<Examples 10-18 and Comparative Examples 3-4> Production of Polyurethane Foam Polymer Polyols (I-1 to I-9) and Comparative Polymer Polyols (Examples 1-9 and Comparative Examples 1-2) R-1 to R-2) were used, and polyurethane foams were produced by the foaming formulation shown below at the blending ratios shown in Tables 3 and 4. The results of measuring the physical properties of these foams are shown in Tables 3 and 4. The foaming formulation is as follows.
[1] The temperature of the polymer polyol, the mixture of polyol (a1-1), and the organic polyisocyanate is adjusted to 25 ± 2 ° C., respectively.
[2] Put polymer polyol, polyol (a1-1), foam stabilizer, water, catalyst in the order of a 1 liter stainless steel beaker, stir and mix at room temperature (25 ° C. ± 2 ° C.), and immediately organic Polyisocyanate was added, and foaming was performed by stirring using a stirrer [Homodisper: manufactured by Tokushu Kika Co., Ltd., stirring conditions: 2000 rpm × 8 seconds].
[3] After the stirring was stopped, the contents were put into a wooden box (25 ° C. ± 2 ° C.) of 25 × 25 × 10 cm to obtain a polyurethane foam.

表３および表４におけるフォーム物性の評価方法は以下の通りである。
密度（ｋｇ／ｍ³）：ＪＩＳ Ｋ６４００−１９９７〔項目５〕に準拠
２５％ＩＬＤ（硬度）（ｋｇｆ／３１４ｃｍ²）
：ＪＩＳ Ｋ６３８２−１９９５〔項目５．３〕に準拠
引張強度（ｋｇｆ／ｃｍ²）：ＪＩＳ Ｋ６３０１−１９９５〔項目３〕に準拠
引裂強度（ｋｇｆ／ｃｍ） ：ＪＩＳ Ｋ６３０１−１９９５〔項目９〕に準拠
切断伸度（％） ：ＪＩＳ Ｋ６３０１−１９９５〔項目３〕に準拠
圧縮永久歪（％） ：ＪＩＳ Ｋ６３８２−１９９５〔項目５．５〕に準拠
なお通常ポリウレタンフォームの物性として、密度は１５〜５０の範囲が好ましく、２５％ＩＬＤ、引張強度、引裂強度、切断伸度は数値が大きいほど好ましい。また、圧縮永久歪は数値が小さいほど好ましい

The evaluation methods of foam physical properties in Tables 3 and 4 are as follows.
Density (kg / m ³ ): Conforms to JIS K6400-1997 [Item 5] 25% ILD (Hardness) (kgf / 314 cm ² )
: Tensile compliant JIS K6382-1995 [Item 5.3] strength (kgf / cm ^2): conforms to JIS K6301-1995 [item 3] Tear strength (kgf / cm): conforms to JIS K6301-1995 [Item 9] Cutting elongation (%): Conforms to JIS K6301-1995 [Item 3] Compression set (%): Conforms to JIS K6382-1995 [Item 5.5] Usually, the density of the polyurethane foam is 15-50. The range is preferable, and 25% ILD, tensile strength, tear strength, and elongation at break are preferably as the numerical value is large. Further, the compression set is preferably as the numerical value is smaller.

  From the results of Tables 1 and 2, it can be seen that Examples 1 to 9 have a smaller particle diameter and a lower viscosity of the polymer in the polymer polyol than Comparative Examples 1 and 2. From the results of Tables 3 and 4, the polyurethane foams of Examples 10 to 18 have a very good 25% ILD, tensile strength, tear strength, and elongation at break, compared with the polyurethane foams of Comparative Examples 3 to 4, and compression. It can be seen that the permanent set is improved.

  The polyurethane resin produced by using the polymer polyol obtained by the production method of the polymer polyol of the present invention is usually used for various uses in which the polyurethane resin is used. It is suitably used for applications such as indoor conditioning. Therefore, the polymer polyol obtained by the method of the present invention is useful as a raw material for polyurethane resins and polyurethane foams.

Claims (5)

In the first step of polymerizing the monomer-containing mixed solution (A1) comprising the polyol (a), the ethylenically unsaturated monomer (d), the radical polymerization initiator (k), and the dispersant (e), a polymer polyol intermediate ( B1), and then polyol (a), ethylenically unsaturated monomer (d), radical polymerization initiator (k), dispersant (e), and base polymer polyol (h1) [ie intermediate (B1)] In the second step of polymerizing the monomer-containing mixed liquid (A2), a method for producing a polymer polyol, the concentration of (d) in (A1) and (A2) before the start of polymerization in each step ( (Mass%) is 7 to 25, the polymer content (mass%) in (h1) is 7 to 25, and the conversion rate (mass%) of the polymer (d) in each step is 80. And from the start of polymerization in (d) The conversion rate (mass%) to coalescence is 80 or more at a conversion rate (mass% / min) up to 80, and the polymer content (mass%) in the resulting polymer polyol (I) is 30 to 45. A method for producing a polymer polyol (I), which is characterized in that it exists. In the first step of polymerizing the monomer-containing mixed solution (A1) comprising the polyol (a), the ethylenically unsaturated monomer (d), the radical polymerization initiator (k), and the dispersant (e), a polymer polyol intermediate ( B1), then polyol (a), ethylenically unsaturated monomer (d), radical polymerization initiator (k), dispersant (e), and base polymer polyol (hi) [ie intermediate (Bi) The monomer-containing mixed solution (Ai + 1) is polymerized to obtain a polymer polyol intermediate (Bi + 1), and (d) is similarly polymerized using (Bi + 1) as the base polymer polyol (hi + 1) in the next step. The process is repeated n-1 times from i = 1 to i = n-1 (where i is an integer from 1 to n-1), and a method for producing a polymer polyol, which is repeated The number n is 3 to 7, the concentration (mass%) of (d) in (A1) and (Ai + 1) before the start of polymerization in each step is 7 to 25, and the polymer content in (hi) (Mass%) is 7-50, and polymer content (mass%) in polymer polyol (I) obtained is 30-65, The manufacturing method of polymer polyol (I) characterized by the above-mentioned . The conversion rate (mass%) of the ethylenically unsaturated monomer (d) to the polymer in each step is 80 or more, and the conversion ratio (mass%) of the polymerization (d) to the polymer is up to 80. The production method according to claim 2, wherein the conversion rate (mass% / min) of is at least 8. The production method according to any one of claims 1 to 3, wherein the content (mass%) of the polyoxyalkylene ether of the α-alkenyl group-containing compound in the ethylenically unsaturated monomer (d) is 2 to 15. A polyol component and a polyisocyanate component, 5. The method for producing a polyurethane resin by reacting in the presence of at least one additive selected from a catalyst, a foaming agent, and a foam stabilizer, as at least a part of the polyol component according to claim 1. A process for producing a polyurethane resin, wherein the polymer polyol (I) obtained by the production process is used.