JP2010235903A - Method of producing polymer polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the following problem in a conventional production method: only a polymer polyol having a volume average particle size of the polymer of 1 &mu;m or above is obtained, and therefore hardness, cutting elongation and tear strength of a urethane resin (for example, a urethane foam) using the polymer polyol are inadequate. <P>SOLUTION: In a method of producing the polymer polyol prepared by dispersing polymer particles in the polyol (C), the production method has a step (I) of dispersing a thermoplastic polymer (A) in the polyol (C) at 80-200&deg;C in the presence of a dispersant (E) and optionally in the presence of a thermoplastic agent (F), further, using at least one dispersion mixer (B) selected from a group consisting of a rotary dispersion mixer and a high-pressure dispersion mixer. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a polymer polyol.

  Conventionally, as a method of dispersing a polymer in a polyol, a preformed polymer resin and a polyol are formed in a single mixer to form an initial dispersion in which the polymer resin is dispersed in the polyol. A method (for example, refer to Patent Document 1) including a step of contacting under conditions of sufficient heat and sufficient shearing force is known.

JP 2004-510855 A

  However, in the conventional method, in the polymer polyol obtained by the method, only a polymer having a volume average particle diameter of 1 μm or more can be obtained. As a result, the urethane resin (for example, urethane foam) using the polymer polyol has insufficient hardness, elongation at break and tear strength.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a method for producing a polymer polyol in which polymer particles are dispersed in a polyol (C), in which a thermoplastic polymer (A) is mixed with a rotary dispersion mixing apparatus in the presence of a dispersant (E). And a step (I) of dispersing in the polyol (C) at 80 ° C. to 200 ° C. using at least one dispersion mixing device (B) selected from the group consisting of a high-pressure dispersion mixing device. Is the gist.
The present invention also relates to a method for producing a polymer polyol in which polymer particles are dispersed in a polyol (C), wherein the thermoplastic polymer (A) is added in the presence of the dispersant (E) and the plasticizer (F). A step of dispersing in polyol (C) at 80 ° C. to 200 ° C. using at least one dispersion mixing device (B) selected from the group consisting of a rotary dispersion mixing device and a high-pressure dispersion mixing device (I) ).

  By the production method of the present invention, a polymer polyol having a volume average particle diameter of the polymer of less than 1 μm is obtained. And the urethane resin (for example, urethane foam) using the polymer polyol of the present invention has sufficient hardness, cut elongation and tear strength of the urethane resin.

  In the production method of the present invention, the thermoplastic polymer (A) is dispersed in the polyol (C) using the dispersion mixing device (B). The dispersion device (B) is at least one dispersion mixing device selected from the group consisting of a rotary dispersion mixing device (B1) and a high pressure dispersion mixing device (B2).

  The main dispersion principle of (B1) is that the particles are pulverized and dispersed by applying a shearing force to the particles from the outside by rotation of the drive unit or the like. Moreover, (B1) can be operated under normal pressure or under pressure. Rotation is preferred as the drive mode of the drive unit.

  As the rotary dispersion mixing device (B1), TK homomixer (manufactured by PRIMIX Co., Ltd.), CLEARMIX (manufactured by MTECHNIC Co., Ltd.), Philmix (manufactured by PRIMIX Corporation), Ultra Turrax (IKA Corporation )), Ebara Milder (manufactured by Ebara Manufacturing Co., Ltd.), Cavitron (manufactured by Eurotech), biomixer (manufactured by Nippon Seiki Co., Ltd.), and the like.

As the high-pressure dispersion mixing apparatus (B2), by passing the constricted portion at a high speed while maintaining the dispersion at a high pressure, particles existing in the dispersion can be further removed by the shearing force generated at that time or the impact force due to cavitation. It has a fine dispersion mechanism.
(B2) includes, in addition to the above mechanism, a mechanism in which a mechanism that causes the solution that has passed through the throttle in the mechanism to collide with a substrate such as diamond is added, or two throttles that face the aqueous dispersion A device having a mechanism for ejecting and colliding is also applicable.

  Examples of the high-pressure dispersion mixer (B2) include an ultra-high pressure homogenizer (manufactured by IKA), a microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), a high-pressure homogenizer (manufactured by Niro Soabi), and a Gaurin homogenizer (manufactured by Gaulin). Is exemplified.

  As the dispersion mixing device (B), two or more types of devices selected from the group consisting of (B1) and (B2) may be used in combination.

  The thermoplastic polymer (A) includes polyvinyl resin (A-1), polyester resin (A-2), polyamide resin (A-3) and the like.

  Polyvinyl resin (A-1) is obtained by (co) polymerizing the following vinyl monomers (m1) to (m7) by known polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.). Resin.

(M1) Aliphatic hydrocarbon vinyl monomer Alkene (ethylene, propylene, 1-octene, etc.) having 2 to 30 (preferably 2 to 12, more preferably 2 to 10) carbon atoms and 4 to 30 (preferably 4) carbon atoms. -12, more preferably 4-5) alkadienes (such as butadiene and isoprene).
(M2) Aromatic vinyl monomer Styrene and its derivatives, for example, styrene (hereinafter abbreviated as St), o-, m- or p-alkyl (1 to 10 carbon atoms) styrene (vinyl toluene, etc.), α-alkyl ( C1-C10) Styrene (α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).

(M3) (meth) acrylic monomer alkyl (carbon number 1 to 20) (meth) acrylate {methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.}, mono- or di-alkyl (carbon number) 1-4) Aminoalkyl (2 to 4 carbon atoms) (meth) acrylate {dimethylaminoethyl (meth) acrylate and the like}, (meth) acrylonitrile, (meth) acrylamide and the like.
Note that (meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter. Similarly, (meth) acrylonitrile and (meth) acrylamide mean methacrylonitrile and / or acrylonitrile (hereinafter, acrylonitrile is abbreviated as ACN), and methacrylamide and / or acrylamide, respectively.

(M4) Other unsaturated mono- or di-carboxylic acids Unsaturated mono- or di-carboxylic acids having 2 to 30 carbon atoms (preferably 3 to 20 and more preferably 4 to 15), etc. [crotonic acid and maleic acid , Fumaric acid, itaconic acid and the like] and derivatives thereof [mono- or di-alkyl (C1-20) ester, acid anhydride (maleic anhydride etc.) and imide (maleic imide etc.), etc.].
(M5) Carboxylic acid ester of unsaturated alcohol Carboxylic acid (C2-C4) ester (vinyl acetate etc.) such as vinyl alcohol and (meth) allyl alcohol.
(Meth) allyl means methallyl and / or allyl, and the same applies hereinafter.
(M6) Alkyl ethers of unsaturated alcohols Alkyl (C1-20) ethers such as vinyl alcohol and (meth) allyl alcohol.
(M7) Halogen-containing vinyl monomer Vinyl chloride, vinylidene chloride, chloroprene and the like.

  (A-1) includes polyolefin resin (A11), polystyrene resin (A12), acrylic resin (A13), fluororesin (A14) and the like.

  (A11) includes one or more (co) polymers of alkenes and one or more of alkenes and one or more of (m2) to (m7) (weight ratio: 5/95 to 95/5, preferably 50 Copolymer (A111); and one or more (co) polymers of alkadiene and a copolymer of alkadiene and one or more of (m2) to (m7) (A112) Etc. are included.

(A111) includes polypropylene, polyethylene, ethylene / propylene copolymer, propylene and / or copolymer of ethylene and one or more of other alkenes (random or block), ethylene / vinyl acetate copolymer (EVA) And ethylene / ethyl acrylate copolymer (EEA).
Among (A111), polypropylene, polyethylene, and ethylene / propylene copolymer are preferable from the viewpoint of the particle diameter of the polymer.
Examples of (A112) include polybutadiene rubber (BR), St / butadiene rubber (SBR), polyisoprene rubber (IR), ACN / butadiene rubber (NBR), butyl rubber (IIR), and the like. Therefore, SBR is preferable.

  As (A12), one or more (co) polymers of (m2) and one or more of (m2) and one or more of (m3) to (m7) (weight ratio: 5/95 to 95/5) , Preferably 50/50 to 90/10) and the like.

  (A12) is a copolymer of polystyrene, polyvinyltoluene and (m2) and at least one monomer selected from the group consisting of methyl methacrylate, ACN and butadiene [St / ACN copolymer (AS resin), ACN / Butadiene / St copolymer (ABS resin), St / methyl methacrylate / ACN copolymer, methyl methacrylate / butadiene / St copolymer (MBS resin) and the like].

  (A13) includes (m3) one or more (co) polymers (polymethyl methacrylate, polybutyl acrylate, etc.) and one or more (m3) and one or more (m4) to (m7) ( And a copolymer with a weight ratio of 5/95 to 95/5, preferably 50/50 to 90/10).

  Examples of the fluororesin (A14) include a binary copolymer of vinylidene fluoride and hexafluoropropylene, a terpolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, and (m1) and tetrafluoroethylene. The alternating copolymer of these is mentioned.

  Examples of the polyester resin (A-2) include polyethylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate by polycondensation of diols such as ethylene glycol, butylene glycol, and cyclohexanedimethanol, and dicarboxylic acids such as terephthalic acid and adipic acid. Examples thereof include aliphatic polyesters such as aromatic polyester, polybutylene adipate and polyethylene adipate, and aliphatic polyesters such as poly-ε-caprolactone by ring-opening polymerization such as ε-caprolactone.

  The polyamide resin (A-3) includes nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 610, 11-amino by polycondensation of hexamethylenediamine and sebacic acid. Nylon 11 by polycondensation of undecanoic acid, nylon 12 by ring-opening polymerization of ω-laurolactam or polycondensation of 12-aminododecanoic acid, and copolymer nylon containing two or more components of the nylon .

  Of these polymers, (A1) is preferable from the viewpoint of little influence on the physical properties of the urethane foam.

  The viscosity at 140 ° C. of (A) is preferably 2,000,000 mPa · s or less from the viewpoint of the particle diameter of the polymer.

  As the polyol (C), a known polyol (Japanese Patent Laid-Open No. 2007-191682 and Japanese Patent Laid-Open No. 2004-002800 (corresponding US patent application: US2005 / 245724A1) and the like) used for the production of a polymer polyol can be used. For example, at least 2 (preferably 2 to 8 from the viewpoint of physical properties of the polyurethane resin) active hydrogen-containing compounds (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.) and alkylene oxide (hereinafter referred to as “polyhydric alcohol”) , Abbreviated as AO) and the compound (c1) having a structure added thereto and a mixture thereof. From the viewpoint of productivity at the time of polyurethane production, among these, from the viewpoint of mechanical properties of the polyurethane resin obtained, a compound having a structure in which AO is added to a polyhydric alcohol is preferable.

  Examples of polyhydric alcohols include dihydric alcohols having 2 to 20 carbon atoms {aliphatic diols (for example, ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). And alicyclic diols (for example, cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol), trihydric alcohols having 3 to 20 carbon atoms {aliphatic triols (for example, glycerin, trimethylolpropane, trimethylol). Alkanetriols such as methylolethane and hexanetriol}; 4-8 or higher polyhydric alcohols having 5 to 20 carbon atoms {aliphatic polyols (for example, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerides) And intramolecular or intermolecular dehydration products of alkane polyols and their or alkane triol, such as dipentaerythritol; and sucrose, glucose, mannose, fructose and sugar and their derivatives such as methyl glucoside)} and the like.

  Polyhydric (2 to 8 or more) 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 (novolak) For example, polyphenols described in US Pat. No. 3,265,641.

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).
As polyamines (number of primary and secondary amino groups: 2 to 8 or more), aliphatic amines, alkylene diamines having 2 to 6 carbon atoms (for example, ethylene diamine, propylene diamine and hexamethylene diamine), carbon Examples thereof include polyalkylene polyamines having a number of 4 to 20 (such as dialkylenetriamines, trialkylenetetramines, tetraalkylenepentamines, pentaalkylenehexamines, and hexaalkyleneheptamines having 2 to 6 carbon atoms in the alkylene group).
Moreover, as a polyamine, C6-C20 aromatic polyamine (For example, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, and diphenyletherdiamine); C4-C20 alicyclic Examples include polyamines (for example, isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine); heterocyclic polyamines having 4 to 20 carbon atoms (for example, piperazine and aminoethylpiperazine), and the like.
As monoamine, ammonia; as aliphatic amine, 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 alicyclic monoamine (for example, cyclohexylamine); C4-C20 heterocyclic monoamine (for example, piperidine) and the like.

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

  Of these active hydrogen-containing compounds, polyhydric alcohols are preferred from the viewpoint of mechanical properties of the resulting polyurethane resin.

  As the AO added to the active hydrogen-containing compound, those having 2 to 8 carbon atoms are preferable from the viewpoint of the physical properties of the polyurethane resin, and ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1 , 2-, 1,3-, 1,4- and 2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide (hereinafter abbreviated as SO), and combinations of two or more thereof (block and / or Or random addition). From the viewpoint of physical properties of the polyurethane resin, PO or a combination of PO and EO (EO content is 25% by weight or less) is preferable.

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, PO and other AO (preferably EO). Examples thereof include those added in the following manner, and esterified products of these addition compounds with polycarboxylic acid or phosphoric acid.
(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

  As other polyols, a nitrogen-containing bond-containing unsaturated polyol in which the above-mentioned polyol and a monofunctional active hydrogen compound having at least one ethylenically unsaturated group are bonded via a polyisocyanate [Japanese Patent Laid-Open No. 2002-308920 ( Corresponding US Pat. No. 6,756,414) and the like described as reactive dispersants {including (c2) described later}] can be used, and from the viewpoint of the particle size of the polymer, the unsaturated polyol (c2) described later is preferable.

  (C2) 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 (c2), the same as those exemplified as the above (c1) can be used. (P) and (c1) may be the same or different.
The number of hydroxyl groups in one molecule of (p) is preferably at least 2, and from the viewpoint of dispersion stability of polymer particles in (c1), more preferably 2 to 8, and further preferably 3 to 3. The number is 4 and the hydroxyl equivalent of (p) is preferably 1,000 to 3,000, more preferably 1,500 to 2,500, from the viewpoint of dispersion stability.

  (Q) used to obtain (c2) 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 a polymer forming polymer fine particles, and the number of ethylenically unsaturated groups in one molecule is 1 to 3, One is particularly 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, and alkenyl side chain group. Examples thereof include phenol, unsaturated polyether monool, and the like.

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.
As monoesters of unsaturated monocarboxylic acid and dihydric alcohol, for example, C3-8 unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid and the dihydric alcohol (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 include propyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate.

Examples of monoesters 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 unsaturated polyether monools include 1 to 50 moles of adducts of the above monohydroxy-substituted unsaturated hydrocarbons or phenols having an alkenyl side chain group (C2-8) [for example, polyoxyethylene (degree of polymerization 2 to 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 an 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 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, polyhydric, and higher polyhydric alcohols or polyesters with unsaturated carboxylic acids [ For example, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, and the like.

From the viewpoint of dispersion stability, preferred compounds among these are C3-6 alkenol, monoester of C3-8 unsaturated monocarboxylic acid and C2-12 dihydric alcohol, and phenol having an alkenyl side group. More preferably, 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 1,000 or less, 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 of these 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); Phosgenates of a mixture with a polyamine having 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.
Of these, aromatic diisocyanates are preferable from the viewpoint of physical properties of the polyurethane resin, and 2,4- and / or 2,6-TDI is more preferable.

The nitrogen-containing bond of (c2) 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.

(C2) is a ratio such that the average value of the 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, as determined by the following formula. , (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, and 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.

  As the dispersant (E), various types having a number average molecular weight (hereinafter abbreviated as Mn) of 1,000 or more (preferably 1,000 to 10,000), for example, known in the production of polymer polyols are known. (As described in JP 2005-162791 A and JP 2004-002800 A (corresponding US patent application: US 2005/245724 A1)), acid-modified polyolefins, and the like can be used (E ) Includes reactive dispersants having an ethylenically unsaturated group that can copolymerize with St or ACN, and non-reactive dispersants that do not copolymerize with St or ACN.

Specific examples of the dispersant (E) include: [1] At least a part of the hydroxyl group of the polyol is reacted with methylene dihalide and / or ethylene dihalide to increase the molecular weight, and the reaction product is further mixed with an ethylenically unsaturated group. Ethylenically unsaturated group-containing modified polyol obtained by reacting a 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. A graft polymer having a polymer fine particle affinity segment of 0.0 or less as a main chain (Japanese Patent Laid-Open No. 05-059134) (3) Graft type dispersants in which polyols and oligomers are combined; [3] High molecular weight by reacting at least part of polyol hydroxyl groups with methylene dihalide and / or ethylene dihalide High molecular weight polyol type dispersants such as modified polyols (described in JP-A-07-196749, etc.); [4] Number average molecular weight is 1,000 to 1,000,000, at least a part thereof Dispersion of oligomer type such as vinyl oligomers, which are soluble in polyols, and dispersants (for example, JP 09-77968 A), which use the oligomers together with the above-mentioned [1] modified polyether polyols containing ethylenically unsaturated groups Agent. Including (e1) described later}; [5] Acid-modified polyolefin and the like.
Among these, [1], [4] and [5] are preferable from the viewpoint of the particle diameter of the polymer, and [5] is more preferable.

Among these, the following (e1) and (e2) are particularly preferable from the viewpoint of the particle diameter of the polymer.
(E1) A vinyl oligomer having a number average molecular weight of 1,000 to 1,000,000.
(E2) Acid-modified polyolefin

  (E1) is a vinyl oligomer obtained by polymerizing an ethylenically unsaturated compound. As the ethylenically unsaturated compound constituting (e1), the same vinyl monomers (m1) to (m7) as described above can be used.

Mn of (e1) is 1,000 to 1,000,000, preferably 100,000 to 950, based on polystyrene by gel permeation chromatography (GPC) measurement from the viewpoint of the particle diameter of the polymer particles. 000, more preferably 150,000 to 900,000, particularly preferably 200,000 to 250,000. In addition, (e1) is soluble in the polyol (C) from the viewpoint of the particle diameter of the polymer [a mixture in which 5% by weight of (e1) is uniformly mixed in (C) based on the total weight of (e1) and (C). It is desirable that the transmittance of the laser beam is 10% or more.
In addition, Mn of (e1) 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 the sediment, and is defined as Mn of (e1).

  The production of (e1) can be carried out by a usual polymerization method of ethylenically unsaturated compounds, except that the degree of polymerization is adjusted so that the number average molecular weight is 1,000 to 1,000,000. For example, a vinyl monomer is polymerized in the presence of a known radical polymerization initiator, if necessary, in a solvent. Moreover, (e1) may be obtained by polymerizing a vinyl monomer in the polyol (C). In this case, the polymerization concentration is preferably 1 to 40% by weight, more preferably 5 to 20% by weight. 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 all vinyl monomers.

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 and n-butanol. 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 (such as dodecyl mercaptan and mercaptoethanol), alcohols (such as isopropyl alcohol, methanol and 2-butanol), halogenated hydrocarbons (such as carbon tetrachloride, carbon tetrabromide and chloroform) 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 is also performed under atmospheric pressure or under pressure. Can do.

(E2) is obtained by adding ethylenically unsaturated dicarboxylic acid (s) to polyolefin (t). Examples of (s) include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides thereof. Of these, maleic anhydride is preferred from the viewpoint of the particle size of the polymer.
Polyolefin (t) includes polyethylene resin [high-density polyethylene, medium-density polyethylene, low-density polyethylene and ethylene and one or more other vinyl compounds (α-olefin, vinyl acetate, methacrylic acid, acrylic acid, etc.). Copolymer, etc.], polypropylene resins (polypropylene and copolymers of propylene and one or more other vinyl compounds, etc.), polybutene, poly-4-methylpentene-1, and mixtures of two or more thereof. It is done.
The number average molecular weight of the polyolefin (t) is preferably from 500 to 100,000, more preferably from 1,000 to 20,000, from the viewpoint of the particle diameter of the polymer.
Also preferred among the polyolefins (t) is a low molecular weight polyolefin resin obtained by thermal degradation of a high molecular weight polyolefin. In particular, from the viewpoint of the particle size of the polymer, a low molecular weight polyethylene resin obtained by a thermal degradation method is more preferable. The Mn of such low molecular weight polyethylene is 1,000 to 20,000.
The amount of the ethylenically unsaturated dicarboxylic acid (s) added to the polyolefin (t) is preferably 0.5 to 30% by weight from the viewpoint of the particle diameter of the polymer based on the weight of the obtained (e2). More preferably, it is 1 to 20% by weight. The amount added to (t) of (s) is preferably 0.5 to 30% by weight, more preferably 1 to 20% from the viewpoint of the particle diameter of the polymer based on the weight of (e2) obtained. % By weight.

  The amount of the dispersant (E) used is preferably 5 to 15% by weight, more preferably 5 to 10% by weight, from the viewpoint of the particle size of the polymer with respect to the thermoplastic polymer (A).

  As the plasticizer (F), known plasticizers for thermoplastic resins can be used, and examples thereof include paraffin, wax, and higher alcohol. Of these, higher alcohols are preferred from the viewpoint of compatibility with (A) and (C). Examples of higher alcohols include oleyl alcohol, stearyl alcohol, cetanol and ralyl alcohol.

  The amount of the plasticizer (F) used is preferably less than 25% by weight, more preferably less than 15% by weight, based on the weight of the polymer polyol, from the viewpoint of the physical properties of the urethane foam.

Below, the manufacturing method of a polymer polyol is demonstrated.
When using the dispersing apparatus (B-1), the polyol (C) is put in a container in advance and the temperature is raised to the temperature during dispersion. The container is not particularly limited, and an open container or a sealed container such as a pressure-resistant autoclave may be used. A thermoplastic polymer (A), a dispersant (E), and a plasticizer (F) as necessary are put into the container, and the temperature is adjusted to the temperature at the time of dispersion. There is no particular limitation on the order of input at this time.
Stirring at a stirring speed of 15000 rpm to 20000 rpm using the apparatus (B-1) while controlling the temperature of what was put into this container. The stirring time is preferably 5 minutes to 30 minutes from the viewpoint of the particle size of the polymer.
Thereafter, the container contents are cooled to obtain a polymer polyol. As the cooling method, from the viewpoint of the particle size of the polymer, a method of cooling while stirring and a method of charging the container contents into liquid nitrogen and cooling are preferable, and a method of charging into liquid nitrogen and cooling is more preferable. is there.

When using the dispersing device (B-2), the polyol (C), the thermoplastic polymer (A) and the dispersing agent (E) and, if necessary, the plasticizer (B) are used in the same manner as when (B-1) is used. F) is put into a container and all ingredients are blended. Thereafter, the container contents are put into (B-2), and the dispersion process is performed in (B-2). The pressure at that time is preferably 100 MPa to 150 MPa from the viewpoint of particle diameter.
After the dispersion treatment, the dispersion-treated product is cooled to obtain a polymer polyol. As the cooling method, from the viewpoint of the particle size of the polymer, a method of cooling while stirring and a method of charging the container contents into liquid nitrogen and cooling are preferable, and a method of charging into liquid nitrogen and cooling is more preferable. is there.

  The amount (% by weight) of the thermoplastic polymer (A) used in the step (I) is determined from the viewpoint of mechanical properties of the polyurethane resin described later and prevention of aggregation of the polymer in the polyol. , Preferably 30 to 60, more preferably 32 to 58, particularly preferably 35 to 56, most preferably, based on the total weight of the polyol (C) and the dispersant (E) and the plasticizer (F) used if necessary. Is 38-55.

  The amount (% by weight) of the polyol (C) used in the step (I) is selected from the viewpoints of preventing aggregation of polymer particles and mechanical properties of the resulting polyurethane resin, and the thermoplastic polymer (A) and polyol (C) in the step (I). ) And dispersant (E) and, if necessary, the total weight of plasticizer (F) used is preferably 40 to 70, preferably 42 to 68, particularly preferably 44 to 65, most preferably 45 to 62. is there.

  The temperature of the step (I) in which the thermoplastic polymer (A) is dispersed in the polyol (C) is 80 ° C. to 200 ° C., and a polymer and a viewpoint that prevent decomposition or deterioration of the polyol (C) as a continuous phase From the viewpoint of the particle size of the polymer in the polyol, it is preferably 120 to 150 ° C, more preferably 130 to 150 ° C, and further preferably 140 to 150 ° C. When it exceeds 200 ° C., the polyol (C), which is a continuous phase, is decomposed and deteriorated. Moreover, if it is less than 80 degreeC, the particle diameter of the polymer in a polymer polyol will become large.

When the step (I) is performed in the presence of the dispersant (E), the interfacial tension between the mixture of the dispersant (E) and the thermoplastic polymer (A) and the polyol (C) is from the viewpoint of the particle diameter of the polymer. In the step (I) temperature, 0 to 4 mN / m is preferable, and 0 to 2 mN / m is more preferable.
When the step (I) is carried out in the presence of the dispersant (E) and the plasticizer (F), a mixture of the dispersant (E), the plasticizer (F) and the thermoplastic polymer (A) and the plasticizer (F) And, from the viewpoint of the particle diameter of the polymer, the interfacial tension with the mixture of polyol (C) is preferably 0 to 4 mN / m, more preferably 0 to 2 mN / m at the temperature of step (I). is there.
The interfacial tension is measured by the following method.

[Measurement method of interfacial tension]
When the step (I) is performed in the presence of the dispersant (E), the dispersant (E) and the thermoplastic polymer (A) are placed in a measurement cell and the temperature is adjusted to a predetermined temperature. The polyol (C) temperature-controlled to predetermined temperature is dripped there while adjusting temperature to predetermined temperature, and it measures with an automatic surface tension meter (the Kyowa Interface Science make; type CB-A3, Wilhelmy method).
When the step (I) is performed in the presence of the dispersant (E) and the plasticizer (F), the dispersant (E), the plasticizer (F), and the thermoplastic polymer (A) are placed in a measurement cell at a predetermined temperature. Adjust the temperature. Separately, a polyol (C) and a plasticizer (F) were mixed at a predetermined temperature with a separate beaker and mixed and dropped while adjusting the temperature to a predetermined temperature, and an automatic surface tension meter (manufactured by Kyowa Interface Science; Measured by format CB-A3, Wilhelmy method).
The amounts of the thermoplastic polymer (A), polyol (C), dispersant (E) and plasticizer (F) used in the measurement of interfacial tension are the weight ratio of these materials used in the method for producing polymer polyol. It is used so that it may become the same weight ratio. Moreover, the usage-amount at the time of using a plasticizer (F) is made so that the quantity put into a cell and the quantity mixed with a polyol (C) become the same quantity.

When the step (I) is performed in the presence of the dispersant (E), the viscosity (mPa · s) of the thermoplastic polymer (A) is 150 at the temperature of the step (I) from the viewpoint of the particle diameter of the polymer. It is preferably ˜2,000,000, more preferably 150 to 200,000, and still more preferably 180 to 350.
When the step (I) is performed in the presence of the dispersant (E) and the plasticizer (F), the viscosity (mPa · s) of the mixture of the plasticizer (F) and the thermoplastic polymer (A) is determined as polymer particles. From the viewpoint of diameter, the temperature in step (I) is preferably 150 to 2,000,000, more preferably 150 to 200,000, and further preferably 180 to 350.
In the above viscosity measurement, the thermoplastic polymer (A), the dispersant (E) and the plasticizer (F) are used in the same weight ratio as the weight ratio of these products used in the method for producing the polymer polyol. Use to be.

When the step (I) is performed in the presence of the dispersant (E), the viscosity (mPa · s) of the polyol (C) is 5 to 200 at the temperature of the step (I) from the viewpoint of the particle diameter of the polymer. It is preferable that it is 50, More preferably, it is 50-100.
When the step (I) is performed in the presence of the dispersant (E) and the plasticizer (F), the viscosity (mPa · s) of the mixture of the plasticizer (F) and the polyol (C) is the particle size of the polymer. From the viewpoint, the temperature in the step (I) is preferably 5 to 200, more preferably 50 to 100.
In addition, the usage-amount of a polyol (C) and a plasticizer (F) in the measurement of said viscosity is used so that it may become the same weight ratio as the weight ratio of these things used in the manufacturing method of a polymer polyol.

  In the method for producing a polymer polyol of the present invention, from the viewpoint of the particle diameter of the polymer, the following value L is preferably 0.02 or less, more preferably 0.0002 to 0.018, and still more preferably 0.002 to 0.013.

L is a value determined from the following formula (1) when viscosity A / viscosity C ≧ 1, and from the following formula (2) when viscosity A / viscosity C <1.
L = interface tension / viscosity A / linear velocity × (viscosity A / viscosity C) ^0.84 (1)
L = Interfacial tension / viscosity A / linear velocity × (viscosity A / viscosity C) ^−0.84 (2)

  In the calculation of the value of L, the viscosity A (mPa · s) is the viscosity of the thermoplastic polymer (A) at the temperature of the step (I) when the step (I) is performed in the presence of the dispersant (E). Meaning that when step (I) is carried out in the presence of dispersant (E) and plasticizer (F), the viscosity of the mixture of plasticizer (F) and thermoplastic polymer (A) at the temperature of step (I) Means.

  In the calculation of the value of L, the viscosity C (mPa · s) means the viscosity of the polyol (C) at the temperature of the step (I) when the step (I) is performed in the presence of the dispersant (E). When the step (I) is carried out in the presence of the dispersant (E) and the plasticizer (F), it means the viscosity of the mixture of the plasticizer (F) and the polyol (C) at the temperature of the step (I).

  In calculating the value of L, the interfacial tension is a mixture of the dispersant (E) and the thermoplastic polymer (A) at the temperature of the step (I) when the step (I) is performed in the presence of the dispersant (E). Means the interfacial tension between the polyol (C) and the step (I) in the presence of the dispersant (E) and the plasticizer (F), the dispersant (E) at the temperature of the step (I), It means the interfacial tension between the mixture of plasticizer (F) and thermoplastic polymer (A) and the mixture of plasticizer (F) and polyol (C).

In the calculation of the value of L, the linear velocity (m / s) is 2NDπ {N = rotational speed (times / s), D = radius of stirring blade (m)} when the dispersing device is a rotary dispersion mixing device. In the case where the dispersion apparatus is a high-pressure dispersion mixing apparatus, it means the supply rate (m ³ / s) / average cross-sectional area (m ² ) of the pipe.

  You may add a polyol further to the polymer polyol (D) obtained by the manufacturing method of this invention as needed. In this case, the polyol (C) can be used as the polyol to be added.

Examples of other additives include a solvent. Examples include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, isopropyl alcohol, n-butanol and the like.
Of these solvents, toluene, xylene, isopropyl alcohol, and n-butanol are preferable from the viewpoint of viscosity and mechanical strength of the polyurethane resin to be produced.
When other additives are added, they can be added and mixed by a known method.

  The shape of the polymer particles contained in the polymer polyol obtained by the production method of the present invention is not particularly limited, and may be any shape such as a spherical shape, a spheroid shape, a flat plate shape, etc. From the viewpoint of mechanical properties of the polyurethane resin, the spherical shape is preferable.

The volume average particle diameter (R) (μm) of the polymer particles is preferably 0.1 to 0.9, more preferably 0.25 to 0.8, from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane resin. More preferably, it is 0.3-0.7, Most preferably, it is 0.4-0.6.
The volume average particle diameter is measured by the method described later.

The polymer particle content (% by weight) in the polymer polyol is preferably 30 to 60, more preferably 32 to 58, and particularly preferably 35, from the viewpoint of mechanical properties of the polyurethane resin described later and prevention of aggregation of the polymer in the polyol. ~ 56, most preferably 38-55.
In addition, polymer particle content (weight%) is measured by the method mentioned later.

  The content (% by weight) of the polyol (C) in the polymer polyol is preferably 40 to 70, preferably 42 to 68, particularly preferably 44, from the viewpoint of preventing aggregation of polymer particles and mechanical properties of the resulting polyurethane resin. ~ 65, most preferably 45-62.

  The polymer particle content (% by weight) is measured by the following method.

<Polymer particle content (% by weight)>
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 (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 dried sediment is weighed, and the weight is defined as (W6). The value calculated by the following formula is the polymer particle content (% by weight).

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

  In the present invention, the arithmetic standard deviation of the particle diameter of the polymer particles is preferably 0.6 or less, from the viewpoint of ease of production of the polymer polyol, mechanical properties of the polyurethane resin, and reduction in clogging of the polyurethane resin production apparatus, Preferably it is 0.1 to 0.6, then 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 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). In addition, the volume-based particle size distribution in the measurement and calculation is divided into a range of 0.040 to 262 μm by 65 (0.040 to 0.044 μm, 0.044 to 0.050 μm, 0.051 to 0.057 μm,. 058-0.066 μm, 0.067-0.075 μm, 0.076-0.086 μm, 0.087-0.099 μm, 0.100-0.114 μm, 0.115-0.130 μm, 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, 0. 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, 11.65 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 .234-44.937 μm, 44.3838-51.470 μm, 51.471-58.952 μm, 58.953-67.522 μm, 67.523-77.338 μm, 77.339-88.582 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 0.074 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 polymer polyol obtained by the production method of the present invention can be used as a polyol used for production of polyurethane (polyurethane elastomer, polyurethane foam, etc.). That is, a polymer polyol obtained by the production method of the present invention or a polyol component (Po) containing the polymer polyol and an isocyanate component (Is) comprising a polyisocyanate are converted into a known method (for example, a method described in JP-A No. 2004-263192). ) And the like to obtain a polyurethane.

  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 weight and weight ratio, respectively, unless otherwise specified.

The composition of raw materials, mixing apparatus, symbols, etc. used in Examples and Comparative Examples are as follows.
(1) Thermoplastic polymer (A-1): low molecular polyethylene, number average molecular weight = 2000 [trade name “Sun Wax 151P”, manufactured by Sanyo Chemical Industries, Ltd.]
(A-2): Low-density polyethylene, [trade name “Sumikasen G807”, manufactured by Sumitomo Chemical Co., Ltd.]
(2) Dispersion mixing apparatus (B-1) CLEARMIX [MME TECHNIQUE CO., LTD.]. Agitation blade diameter = 1.2 cm.
(B-2) Ultra high pressure homogenizer [manufactured by IKA]. Average cross-sectional area of the tube = 1 cm ² .
(3) Polyol (C-1): Polyol having a hydroxyl value of 32 and a terminal EO unit content of 14% by weight added to pentaerythritol in the order of PO-EO (terminal primary conversion rate = 74 mol%) [ [Product name “Polyol 50”, manufactured by Sanyo Chemical Industries, Ltd.] 0.14 mol and 0.07 mol of 2-hydroxymethacrylate jointed with 0.16 mol of TDI = 20, number of unsaturated groups / Nitrogen-containing bond-containing unsaturated polyol having a nitrogen-containing group number of 0.22 (see JP 2002-308920 A)
(C-2): Polyol having a hydroxyl value of 56 and an internal EO unit content of 5.5% (terminal primary ratio = 2 mol%) obtained by block addition of glycerin in the order of PO-EO-PO [Sanniks (registered trademark) GP-3030, manufactured by Sanyo Chemical Industries, Ltd.]
(3) Dispersant (E-1): Maleic anhydride modified polyethylene, number average molecular weight = 3300 [trade name “Yumex-2000”, manufactured by Sanyo Chemical Industries, Ltd.]
(4) Plasticizer (F-1): oleyl alcohol [trade name “Angiecol 90N”, manufactured by Shin Nippon Rika Co., Ltd.]
(4) Polyisocyanate TDI-80: Trade name “Coronate T-80” [manufactured by Nippon Polyurethane Industry Co., Ltd.]
(5) 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.]
(6) Foam stabilizer Product name “SRX-280A” (polyether siloxane polymer) [manufactured by Toray Dow Corning Silicone Co., Ltd.]

The measurement and evaluation methods in the examples are as follows.
<Volume average particle diameter>
The obtained polymer polyol was diluted with the polyol used for the production so that the laser light transmittance was 70 to 90%, and the volume average particle size (μm) was measured with the following particle size distribution analyzer. .
Apparatus: 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 J-th particle size (μm)

Example 1 [Production of polymer polyol (D-1)]
[First Step] A polyol (C-1) and a polyol (C-2) are charged in a 1 L SUS container, and the temperature is raised to 140 ° C. which is a dispersion temperature. Separately, a 1 L SUS container was prepared, and the thermoplastic polymer (A-1) and the dispersant (E-1) were dissolved by heating up to 140 ° C., the dispersion temperature, by adding the parts shown in Table 1. The whole amount was charged and stirred for 15 minutes at a dispersion temperature of 140 ° C. and a rotation speed of 20,000 rpm using the dispersion mixing apparatus (B-1).
[Second Step] The product obtained in Step (I) was put into liquid nitrogen and cooled to obtain a polymer polyol (D-1).
Volume average particle diameter of (D-1), interfacial tension {mixture of 30 parts of (A-1) and 2.6 parts of (E-1) and 51 parts of polyol (C-1) and polyol (C-2) 19 Interfacial tension at a dispersion temperature (140 ° C.) with a mixture of parts}, viscosity at a dispersion temperature (140 ° C.) of (A-1) and (C-1) (in the table, described as viscosity A and viscosity C, respectively) Table 2 shows the measurement results.

Example 2 [Production of polymer polyol (D-2)]
[First Step] A polyol (C-1) and a polyol (C-2) are charged in the number of parts shown in Table 1 into a 1 L SUS container, and the temperature is raised to 140 ° C. which is a dispersion temperature. Separately, a 1 L SUS container is prepared, and the thermoplastic polymer (A-1) and the dispersant (E-1) are added in the amounts shown in Table 1 and heated to a dispersion temperature of 140 ° C. and dissolved. Add the entire amount. This was thrown into a dispersing apparatus (B-2) to which a pressure of 150 MPa was applied at a rate of 0.002 m ³ / s to perform a dispersion treatment.
[Second Step] The product obtained in Step (I) was put into liquid nitrogen and cooled to obtain a polymer polyol (D-2).
Volume average particle diameter of (D-2), interfacial tension {mixture of 30 parts of (A-1) and 2.6 parts of (E-1), 51 parts of polyol (C-1) and polyol (C-2) 19 Interfacial tension at a dispersion temperature (140 ° C.) with a mixture of parts}, viscosity at a dispersion temperature (140 ° C.) of (A-1) and (C-1) (in the table, described as viscosity A and viscosity C, respectively) Table 2 shows the measurement results.

Example 3 [Production of polymer polyol (D-3)]
[First Step] A polyol (C-1) and a polyol (C-2) are charged in the number of parts shown in Table 1 into a 1 L SUS container, and the temperature is raised to 140 ° C. which is a dispersion temperature. Separately, a 1 L SUS container is prepared, and the thermoplastic polymer (A-1), the dispersant (E-1) and the plasticizer (F-1) are added in the number of parts shown in Table 1 to obtain the dispersion temperature. The whole solution was heated up to 140 ° C. and dissolved, and stirred for 15 minutes at a dispersion temperature of 140 ° C. and a rotation speed of 20,000 rpm using a dispersion mixing apparatus (B-1).
[Second Step] The product obtained in Step (I) was put into liquid nitrogen and cooled to obtain a polymer polyol (D-3).
Volume average particle diameter of (D-3), interfacial tension {(A-1) 30 parts, (E-1) 2.6 parts and (F-1) 5.7 parts mixture and polyol (C-1) 51 parts, interfacial tension at a dispersion temperature (140 ° C.) with a mixture of 19 parts of polyol (C-2) and 5.7 parts of (F-1)}, 30 parts of (A-1) and (F-1) 11 Viscosity at a dispersion temperature (140 ° C.) of 4 parts of mixture and viscosity at 140 ° C. of 30 parts of (C-1) and 11.4 parts of (F-1) (in the table, viscosity A and viscosity C, respectively) Table 2 shows the measurement results.

Example 4 [Production of polymer polyol (D-4)]
[First Step] Into a 1 L SUS container, the polyol (C-1) and the polyol (C-2) are added in the number of parts shown in Table 1, and the number of parts shown in Table 1 is added, and the dispersion temperature is raised to 140 ° C. . Separately, a 1 L SUS container was prepared, and the thermoplastic polymer (A-1), the dispersant (E-1) and the plasticizer (F-1) were added in the number of parts described in Table 1 at the dispersion temperature. The whole is heated to a certain 140 ° C. and dissolved. This was charged at a pressure of 150 MPa (B-2) at 0.002 m ³ / s for dispersion treatment.
[Second Step] The product obtained in Step (I) was put into liquid nitrogen and cooled to obtain a polymer polyol (D-4).
Volume average particle diameter of (D-4), interfacial tension {(A-1) 30 parts, (E-1) 2.6 parts and (F-1) 5.7 parts mixture and polyol (C-1) 51 parts, interfacial tension at a dispersion temperature (140 ° C.) with a mixture of 19 parts of polyol (C-2) and 5.7 parts of (F-1)}, 30 parts of (A-1) and (F-1) 11 Viscosity at a dispersion temperature (140 ° C.) of 4 parts of the mixture and a viscosity at a dispersion temperature (140 ° C.) of 30 parts of (C-1) and 11.4 parts of (F-1) (in the table, the respective viscosity Table 2 shows the results of measuring A and viscosity C).

Examples 5 to 8 [Production of polymer polyol (D-5) to (D-8)]
In Examples 1 to 4, polymer polyols (D-5) to (D-8) were obtained in the same manner as in Examples 1 to 4 except that the dispersion temperature was 120 ° C.
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A, and viscosity C of (D-5) to (D-8).

Examples 9 to 12 [Production of polymer polyols (D-9) to (D-12)]
In Examples 1 to 4, polymer polyols (D-9) to (D-12) were obtained in the same manner as in Examples 1 to 4, except that the dispersion temperature was 150 ° C.
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A, and viscosity C of (D-9) to (D-12).

Example 13 [Production of polymer polyol (D-13)]
In Example 1, [Polymer 2] is obtained in the same manner as in Example 1 except that the polymer polyol obtained in Step (I) is cooled to 80 ° C. while stirring to obtain a polymer polyol. -13) was obtained.
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A and viscosity C of (D-13).

Example 14 [Production of polymer polyol (D-14)]
[First Step] A polyol (C-1) and a polyol (C-2) are charged in the number of parts shown in Table 1 into a 1 L SUS container, and the temperature is raised to 140 ° C. which is a dispersion temperature. Separately, a 1 L SUS container was prepared, and the thermoplastic polymer (A-1), the dispersant (E-1) and the plasticizer (F-1) were added in the number of parts described in Table 1 at the dispersion temperature. The entire solution heated up to 140 ° C. and dissolved was charged and stirred for 15 minutes at a dispersion temperature of 140 ° C. and a rotation speed of 20,000 rpm using the dispersion mixing apparatus (B-1).
[Second Step] The product obtained in Step (I) was put into liquid nitrogen and cooled to obtain a polymer polyol (D-14).
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A and viscosity C of (D-14).

Example 15 [Production of polymer polyol (D-15)]
[First Step] A polyol (C-1) and a polyol (C-2) are charged in the number of parts shown in Table 1 into a 1 L SUS container, and the temperature is raised to 140 ° C. which is a dispersion temperature. Separately, prepare a 1 L SUS container, and add the thermoplastic polymer (A-2), the dispersant (E-1) and the plasticizer (F-1) in the number of parts shown in Table 1 at the dispersion temperature. The entire solution heated up to 140 ° C. and dissolved was charged and stirred for 15 minutes at a dispersion temperature of 140 ° C. and a rotation speed of 20,000 rpm using the dispersion mixing apparatus (B-1).
[Second Step] The product obtained in Step (I) was put into liquid nitrogen and cooled to obtain a polymer polyol (D-15).
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A and viscosity C of (D-15).

Comparative Example 1 [Production of polymer polyol (H-1)]
In Example 1, a comparative polymer polyol (H-1) was obtained in the same manner as in Example 1 except that the amount of each charge was the number of parts shown in Table 1.
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A and viscosity C of (H-1).

Comparative Example 2 [Production of polymer polyol (H-2)]
In Example 1, a comparative polymer polyol (H-2) was obtained in the same manner as in Example 1 except that the dispersion temperature was 70 ° C.
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A and viscosity C of (H-2).

Comparative Example 3 [Production of polymer polyol (H-3)]
A comparative polymer polyol (H-3) was obtained in the same manner as in Example 1 except that the dispersion temperature was 250 ° C.
Table 2 shows the results of measuring the volume average particle diameter, interfacial tension, viscosity A and viscosity C of (H-3).

Comparative Example 4 [Production of polymer polyol (H-4)]
(A-1), (C-1), (C-2) and (E-1) are supplied at a rate of 30 parts / minute, 51 parts / minute, 19 parts / minute, 2.6 parts / minute, respectively. Was supplied to a biaxial kneader (manufactured by Kurimoto Seiko Co., Ltd.), and the extruded product was recovered to obtain a comparative polymer polyol (H-4). The temperature of the kneading part of the extruder was 140 ° C., and the rotation speed was 450 rpm.

Examples 16 to 30, Comparative Examples 5 to 8 [Production of polyurethane foam]
The polymer polyols (D-1) to (D-15) obtained in Examples 1 to 15 and the comparative polymer polyols (H-1) to (H-4) obtained in Comparative Examples 1 to 4 were used. A polyurethane foam was produced according to the foaming formulation shown below using the blending ratio shown in Table 3. The physical properties of these foams were evaluated by the following methods. The results are shown in Table 3.
<Foaming prescription>
[1] The temperature of each of the polymer polyol, polyol and polyisocyanate was adjusted to 25 ± 2 ° C.
[2] Polymer polyol, polyol, foam stabilizer, water, and catalyst were charged in a 1L stainless steel beaker and stirred and mixed at 25 ° C ± 2 ° C. Polyisocyanate was immediately added, and a stirrer [homodisper, special (Mixing Co., Ltd.)] (stirring 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 16 to 30 and Comparative Examples 5 to 8 in Table 3>
(1) Density (kg / m ³ ): Conforms to JIS K6400-1997 [Item 5].
(2) 25% ILD (hardness) (kgf / 314 cm ² ): Conforms to JIS K6401-1997.
(3) Tensile strength (kgf / cm ² ): Conforms to JIS K6301-1995 [Item 3].
(4) Tear strength (kgf / cm): compliant with JIS K6301-1995 [Item 9] (5) Elongation at break (%): compliant with JIS K6301-1995 [Item 3]

From the results in Table 2, the following were found.
(1) All Examples 1 to 15 have smaller volume average particle diameters than Comparative Examples 1 to 4.

Moreover, the following was found from the results in Table 3.
(2) Examples 16 to 30 are superior to Comparative Examples 5 to 8 in 25% ILD, tensile strength, and tear strength.

  In addition, as a physical property of a polyurethane foam, it represents that 25% ILD, tensile strength, tear strength, and cutting elongation are so favorable that a numerical value is large.

The polymer polyol obtained by dispersing the thermoplastic polymer in the polyol by the production method of the present invention has a smaller particle size than the polymer polyol obtained by the conventional method, and when used in the production of polyurethane foam, Each physical property can be adjusted with good balance, which is preferable.
The polymer polyol obtained by the production method of the present invention can be used for a wide range of uses as various polyurethane resin raw materials, and is particularly suitably used as a polyurethane foam for automobile interior parts, indoor furniture for furniture, and the like.

Claims (11)

A method for producing a polymer polyol in which polymer particles are dispersed in a polyol (C), in which a thermoplastic polymer (A) is mixed with a rotary dispersion mixer and a high-pressure dispersion mixture in the presence of a dispersant (E). A method for producing a polymer polyol, comprising the step (I) of dispersing in a polyol (C) at 80 ° C. to 200 ° C. using at least one dispersion mixing device (B) selected from the group consisting of devices. The method for producing a polymer polyol according to claim 1, wherein the interfacial tension between the mixture of the dispersant (E) and the thermoplastic polymer (A) and the polyol (C) is 0 to 4 mN / m at the temperature of the step (I). . The method for producing a polymer polyol according to claim 1 or 2, wherein the viscosity of the thermoplastic polymer (A) is 150 to 2,000,000 mPa · s at the temperature of step (I). The method for producing a polymer polyol according to any one of claims 1 to 3, wherein the viscosity of the polyol (C) is 5 to 200 mPa · s at the temperature of the step (I). The value of the following L is 0.02 or less, The manufacturing method of the polymer polyol in any one of Claims 1-4.
L: Value obtained from the following formula (1) when viscosity A / viscosity C ≧ 1, and from the following formula (2) when viscosity A / viscosity C <1. The viscosity A (mPa · s) means the viscosity of the thermoplastic polymer (A) at the temperature of the step (I), and the viscosity C (mPa · s) means the polyol (C) at the temperature of the step (I). The interfacial tension means the interfacial tension between the mixture of the dispersant (E) and the thermoplastic polymer (A) at the temperature of the step (I) and the polyol (C), and the linear velocity (m / s ) Means 2NDπ {N = rotational speed (times / s), D = radius of stirring blade (m)} when the dispersion device is a rotary dispersion mixer, and the dispersion device is a high-pressure dispersion mixer. In this case, it means the supply rate (m ³ / s) / average cross-sectional area (m ² ) of the pipe.
L = interface tension / viscosity A / linear velocity × (viscosity A / viscosity C) ^0.84 (1)
L = Interfacial tension / viscosity A / linear velocity × (viscosity A / viscosity C) ^−0.84 (2) A method for producing a polymer polyol in which polymer particles are dispersed in a polyol (C), in which a thermoplastic polymer (A) is subjected to rotary dispersion mixing in the presence of a dispersant (E) and a plasticizer (F). A step (I) of dispersing in a polyol (C) at 80 ° C. to 200 ° C. using at least one dispersion mixing device (B) selected from the group consisting of an apparatus and a high-pressure dispersion mixing device. A method for producing a polymer polyol. The interfacial tension between the mixture of the dispersant (E), the plasticizer (F) and the thermoplastic polymer (A) and the mixture of the plasticizer (F) and the polyol (C) is 0 to 4 mN / in at the temperature of the step (I). The method for producing a polymer polyol according to claim 6, wherein m is m. The method for producing a polymer polyol according to claim 6 or 7, wherein the viscosity of the mixture of the plasticizer (F) and the thermoplastic polymer (A) is 150 to 2,000,000 mPa · s at the temperature of the step (I). The method for producing a polymer polyol according to any one of claims 6 to 8, wherein the viscosity of the mixture of the plasticizer (F) and the polyol (C) is 5 to 200 mPa · s at the temperature of the step (I). The value of the following L is 0.02 or less, The manufacturing method of the polymer polyol in any one of Claims 6-9.
L: Value obtained from the following formula (1) when viscosity A / viscosity C ≧ 1, and from the following formula (2) when viscosity A / viscosity C <1. The viscosity A (mPa · s) means the viscosity of the mixture of the plasticizer (F) and the thermoplastic polymer (A) at the temperature of the step (I), and the viscosity C (mPa · s) is the step (I ) Means the viscosity of the mixture of the plasticizer (F) and the polyol (C) at the temperature, and the interfacial tension means the dispersant (E), the plasticizer (F) and the thermoplastic polymer (A) at the temperature of the step (I). ) And the plasticizer (F) and polyol (C) mixture, and the linear velocity (m / s) is 2NDπ {N = rotation when the dispersion apparatus is a rotary dispersion mixer. Number (times / s), D = radius of stirring blade (m)}, and when the dispersion device is a high-pressure dispersion mixing device, supply speed (m ³ / s) / average cross-sectional area of the pipe (m ² ).
L = interface tension / viscosity A / linear velocity × (viscosity A / viscosity C) ^0.84 (1)
L = Interfacial tension / viscosity A / linear velocity × (viscosity A / viscosity C) ^−0.84 (2) The method for producing a polymer polyol according to any one of claims 1 to 10, comprising a step (II) of cooling with liquid nitrogen after the step (I).