JP4887318B2 - Polymer polyol - Google Patents

Description

  The present invention relates to polymer polyols. More specifically, the present invention relates to a polymer polyol which is suitable as a raw material for polyurethane (polyurethane foam, polyurethane elastomer, etc.) and has excellent reactivity with isocyanate and imparts excellent mechanical properties to polyurethane.

Conventionally, as a polymer polyol used for the production of polyurethane, for the purpose of improving the mechanical properties of polyurethane, ethylene in a polyol containing a plurality of polyols having a specific number of functional groups, a hydroxyl value, and a polyoxyethylene content at a terminal in a specific ratio is used. Polymer polyols obtained by polymerizing an unsaturated compound (for example, see Patent Document 1), polymer polyols obtained by polymerizing an ethylenically unsaturated compound in a polyol having a specific hydroxyl value (for example, see Patent Document 2), and the like are known. It has been.
Japanese Patent Laid-Open No. 3-81314 JP 2003-226734 A

  However, the above-mentioned conventional polymer polyol has a high viscosity, and there is a problem that, for example, moldability at the time of producing a polyurethane foam is lowered. Therefore, there is a need for a polymer polyol that provides a polyurethane having a low viscosity and excellent mechanical properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to a polymer polyol in which polymer particles (JR) containing an ethylenically unsaturated compound (E) as a constituent unit are contained in a polyol (PL), and a molecule based on a molecular terminal hydroxyl group in (PL). The proportion of the polyol (PL1) having a primary hydroxyl group-containing molecular end represented by the following general formula (1) based on the weight of (PL) is 2 to 10 mol% of the terminal primary hydroxyl group. It is a polymer polyol (A) characterized by being 2 to 10%.
[Wherein, R represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom. ]

The polymer polyol (A) of the present invention has the following effects.
(1) The polyurethane foam produced using the polymer polyol of the present invention is excellent in mechanical properties.
(2) The polymer polyol of the present invention has a low viscosity and, for example, is excellent in moldability when producing a polyurethane foam.

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

  The proportion (%) of St based on the weight of (E) constituting (JR) is preferably from 50 to 90, more preferably from 55 to 80, particularly from the viewpoint of coloring the polymer polyol and reducing the content of coarse particles. Preferably it is 60-75, Most preferably, it is 60-71.

  The proportion (%) of ACN based on the weight of (E) constituting (JR) is preferably from 0.1 to 40, more preferably from 10 to 37, from the viewpoint of the content of coarse particles and reduction in coloration of the polymer polyol. Particularly preferred is 20 to 34, and most preferred is 28 to 34.

  The weight ratio of St to ACN (St: ACN) is preferably 90: 0.1 to 50:40, more preferably 80:10 to 55:37, from the viewpoint of the content of coarse particles and reduction in coloration of the polymer polyol. Particularly preferred is 75:20 to 60:34, most preferred 71:28 to 60:34.

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

Examples of (e1) include C4-10, such as methacrylonitrile.
Examples of (e2) include C8-14, such as α-methylstyrene, hydroxystyrene, chlorostyrene, and the like.
As (e3), C4-27, for example, alkyl such as methyl, butyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl and docosyl (meth) acrylate (alkyl group is C1-24) ) (Meth) acrylate; hydroxy polyoxyalkylene (alkylene group is C2-8) mono (meth) acrylate and the like.
In addition, (meth) acrylate means an acrylate and / or methacrylate, and the same applies to (meth) acrylic acid, (meth) allyl and the like in the following, and the same notation is used hereinafter.

(E4) includes an alkylene oxide adduct of an α-alkenyl group-containing compound and an alkylene oxide adduct of an unsaturated ester having a hydroxyl group. Examples of the alkylene oxide adduct of the α-alkenyl group-containing compound include an alkylene oxide (hereinafter abbreviated as AO) adduct of a C3-24 terminal unsaturated alcohol. Examples of the terminal unsaturated alcohol include allyl alcohol and 2-butene. Examples include -1-ol, 3-buten-2-ol, 3-buten-1-ol, and 1-hexen-3-ol. Examples of the AO adduct of an unsaturated ester having a hydroxyl group include an AO adduct of an unsaturated ester having a C3-24 hydroxyl group. Examples of the unsaturated compound having a hydroxyl group include hydroxyalkyl (C2-12) (meth). Acrylate is included, and examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Of these, an AO adduct of allyl alcohol and an AO adduct of hydroxyalkyl (C2-12) (meth) acrylate are preferable. The number of moles of AO added is preferably 1-9, particularly preferably 1-6, and most preferably 1-3.
Examples of the AO include C2-12, such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3-methyl-tetrahydrofuran ( Hereinafter abbreviated as EO, PO, BO, THF and MTHF), 1,3-propylene oxide, isoBO, C5-12 α-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.), and two or more of these (Random addition and / or block addition).
AO is preferably C2-8, more preferably C2-4, particularly preferably C2-3, and most preferably PO and / or EO.
Moreover, as AO, single use and the combined use of 2 or more types of AO are preferable, More preferably, PO or EO is single and PO and EO are combined.
The Mn of (e4) is preferably 110 to 490, the lower limit is more preferably 120, next more preferably 160, particularly preferably 170, most preferably 180, and the upper limit is more preferably 480, More preferred is 450, particularly preferred is 420, and most preferred is 300. When the Mn is 110 or more, the polymer polyol has a low viscosity, which is preferable in terms of handleability, and the hardness of the polyurethane obtained therefrom is also good. When the Mn is 490 or less, the hardness of the polyurethane obtained using the polymer polyol is good. It is.

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

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

SP value = (ΔE / V) ^1/2

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

  Other ethylenically unsaturated monomers (e5) include C2-24, unsaturated carboxylic acids such as (meth) acrylic acid; aliphatic hydrocarbon monomers such as ethylene and propylene; perfluorooctylethyl methacrylate, perfluorooctyl Fluorine-containing (meth) acrylates such as ethyl acrylate; nitrogen-containing monomers other than unsaturated nitriles such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicones;

  As the polyfunctional monomer (e6), C10-40, for example, bifunctional [divinylbenzene, ethylene di (meth) acrylate, polyalkylene oxide glycol di (meth) acrylate, etc.], trifunctional [pentaerythritol triallyl ether, trimethylol] Propane tri (meth) acrylate, etc.] and tetrafunctional [pentaerythritol tetra (meth) acrylate, etc.] monomers; cyclic olefins such as norbornene, cyclopentadiene, norbornadiene, or diene compounds.

  Among (e1) to (e6), preferred are (e3), (e4) and (e6), and more preferred are (e4) and (e6), in view of the viscosity of the polymer polyol and the physical properties of the polyurethane. Is a PO and / or EO adduct of a terminal unsaturated alcohol, a PO and / or EO adduct of an unsaturated ester having a hydroxyl group, a bifunctional monomer, most preferably a PO adduct of allyl alcohol, hydroxyethyl (meth) Divinylbenzene, PO adduct of acrylate.

  The proportion (% by weight) of the other ethylenically unsaturated monomer (e) in the ethylenically unsaturated compound (E) constituting (JR) is usually 50 or less, the viscosity of the polymer polyol, the dispersion stability and the physical properties of the polyurethane. From this viewpoint, it is preferably 3 to 49.9, more preferably 4 to 35, and particularly preferably 5 to 20.

  In particular, the amount (% by weight) of the polyoxyalkylene ether of the α-alkenyl group-containing compound and the (poly) oxyalkylene ether (e4) of the unsaturated ester having a hydroxyl group is 0.1% based on the weight of (E). Is preferably 10 to 10, more preferably 0.5 to 8, and particularly preferably 1 to 6. Within this range, the polymer polyol has a low viscosity and the polymer polyol of the present invention is easily obtained.

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

The volume average particle diameter (μm) of (JR) is preferably 0.2 to 2.0, more preferably 0.25 to 1.5, and particularly preferably 0.3 from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane. ~ 0.7. The volume average particle diameter is measured by the method described later.
The particle diameter range (μm) of (JR) is preferably 0.1 to 100, more preferably 0.1 to 20, particularly preferably 0.1 to 5, from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane. .

In the polyol (PL) in the present invention, the ratio of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group in (PL) is 2 to 10 mol%, and the general formula (1) below is based on the weight of (PL). The ratio of the polyol (PL1) having a primary hydroxyl group-containing molecular terminal represented by the formula is 2 to 10%.
The proportion of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group in (PL) is preferably 2 to 8 mol%, more preferably 3 to 7 mol%, and most preferably 3.9 to 6.9 mol%. . When the proportion of the primary hydroxyl group at the molecular end is less than 2 mol%, the reactivity of (PL) and the mechanical properties of the resulting polyurethane are deteriorated, and when it exceeds 10 mol%, the moldability of the polyurethane is deteriorated. Here, the ratio of the molecular terminal primary hydroxyl group is obtained by ¹ H-NMR analysis method after esterifying (PL) in advance.

Moreover, the ratio of the weight of (PL1) based on the weight of (PL) is preferably 2 to 8%, more preferably 3 to 7%. When the proportion of (PL1) is less than 2%, the reactivity of (PL) and the mechanical properties of the resulting polyurethane are poor, and when it exceeds 10%, the moldability of the polyurethane is poor.

In the formula, R represents a C1-10 hydrocarbon group which may be substituted with a halogen atom.
Specific examples of R in formula (1) include linear alkyl groups (such as methyl, ethyl and propyl groups), branched alkyl groups (such as isopropyl and 2-ethylhexyl groups), (alkyl-substituted) phenyl groups (phenyl and p -Methylphenyl group etc.), halogen atom substituted alkyl groups (chloromethyl, bromomethyl, chloroethyl and bromoethyl groups etc.), halogen atom substituted phenyl groups (p-chloro- and p-bromophenyl groups etc.), and two or more of these Can be used in combination.

The polyol (PL) in the present invention includes a polyol (PL1) having a primary hydroxyl group-containing molecular terminal represented by the general formula (1) and other polyols (PL2).
(PL1) is an AO adduct of an active hydrogen-containing compound, and is obtained by adding C3 or more 1,2-alkylene oxide (hereinafter abbreviated as 1,2-AO) to terminal active hydrogen, It is a polyol having a primary hydroxyl group-containing molecular end represented by (1).

Examples of the active hydrogen-containing compound include at least two (preferably 2 to 8) active hydrogen-containing compounds (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.) and JP-A 2000-344881. And JP-A-2005-162791, JP-A-2004-018543, JP-A-2006-016611, and the like.
C3- or higher 1,2-AO includes C3-12 or higher 1,2-AO among the aforementioned AOs. Specifically, PO, 1,2-butylene oxide, C5-12 α-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.) and the like can be mentioned. Of these, PO, 1,2-butylene oxide, C5-12 α-olefin oxide, styrene oxide, and epichlorohydrin are more preferable from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane. PO, 1,2-butylene oxide, C5-12 α-olefin oxide, particularly preferably PO, 1,2-butylene oxide, and most preferably PO.

  The preferred range of the hydroxyl equivalent and Mn of (PL1) is the same as (PL) described later.

(PL1) can be produced by adding AO to an active hydrogen-containing compound in the presence of a specific catalyst (α).
Examples of (α) include those described in JP-A-2000-344881 and the like, specifically, a boron or aluminum compound to which a fluorine atom, a (substituted) phenyl group and / or a tertiary alkyl group are bonded. For example, for boron compounds, triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, for aluminum compounds, triphenyl Examples include aluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum, and the like.
Among these, from the viewpoint of the generation of primary hydroxyl group-containing molecular ends and the reaction rate of AO addition, triphenylborane, tris (pentafluorophenyl) borane, triphenylaluminum, tris (pentafluorophenyl) aluminum, and more preferable Are tris (pentafluorophenyl) -borane and -aluminum.
The conditions for addition of AO may be the same as those described in the above publication, for example, usually 0.0001 to 10% of the weight of the ring-opening polymer to be produced, and the reaction rate of AO addition and polyurethane are produced. Preferably, 0.001 to 1% of the above catalyst is used from the viewpoint of reactivity at the time, and the reaction is usually performed at 0 to 250 ° C., preferably from 20 to 180 ° C. from the viewpoint of the reaction rate of AO addition and the mechanical properties of polyurethane. It can be carried out.

As the polyol (PL2), other than (PL1), known polyols used for the production of polymer polyols (for example, described in JP-A-2005-162791, JP-A-2004-018543, JP-A-2006-016611) Can be used.
Specific examples of (PL2) include, for example, an AO adduct of at least two (preferably 2 to 8) active hydrogen-containing compounds (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.). And mixtures thereof. Of these, AO adducts of polyhydric alcohols are preferred from the viewpoint of mechanical properties of polyurethane.

  The AO includes those described above. Among these AOs, C2-8 are preferable from the viewpoint of mechanical properties of polyurethane, and EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran, styrene oxide, and these are more preferable. 2 or more (block addition and / or random addition), particularly preferably PO or a combination of PO and EO [EO content is 25% or less based on the weight of (PL), preferably 1 to 20 %].

Specific examples of the AO adduct include a PO adduct of a known active hydrogen-containing compound (Japanese Patent Laid-Open No. 2005-162791 etc.) and PO and another AO (preferably EO) added in the following manner. , And esterified products of these adducts with polycarboxylic acid or phosphoric acid.
(1) Block added in the order of (PO block)-(Other AO block) (2) [(PO block)-(Other AO block)] Block added in the order of ₂ (3) (Other Block added in the order of (AO block)-(PO block)-(other AO block) (4) block added in order of (PO block)-(other AO block)-(PO block) ( 5) Random addition of PO and other AOs (6) Random and block additions in the order described in US Pat. No. 4,226,756.

  The preferred range of hydroxyl equivalent and Mn of (PL2) is the same as (PL) described later.

The hydroxyl equivalent of (PL) is preferably 200 to 4,000, more preferably 400 to 3,000, from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane.
The hydroxyl group equivalent is calculated by dividing 56100 by the hydroxyl value [weight of the hydroxyl group and equivalent potassium hydroxide in 1 g of sample (mg)] measured according to JIS K1557-1: 2007.

  Mn of (PL) is preferably from 500 to 20,000, more preferably from 1,200 to 15,000, particularly preferably from 2,000 to 9,000, from the viewpoints of mechanical properties of polyurethane, viscosity of polymer polyol, and handling properties. 000.

  The polyol (PL) in the present invention is a proportion of 2 to 10 mol% of the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group in (PL), and the proportion of the polyol (PL1) based on the weight of (PL) of 2 to 2. It is necessary to satisfy all 10%. Even if the proportion of the molecular terminal primary hydroxyl group is within the range, if the proportion of (PL1) is less than the lower limit of the range, the moldability is deteriorated and the air permeability of the polyurethane foam is deteriorated. Even if the ratio of (PL1) is within this range, if the ratio of the molecular terminal primary hydroxyl group is not less than the upper limit of the range, the moldability is deteriorated and the air permeability of the polyurethane foam is deteriorated.

  The content (% by weight) of the polymer particles (JR) in the polymer polyol (A) is preferably 35 to 60 based on the weight of (A) from the viewpoint of mechanical properties of polyurethane and prevention of aggregation of (JR). More preferably, it is 38-58, Most preferably, it is 40-55, Most preferably, it is 46-52. In addition, content of (JR) in (A) is measured by the method mentioned later.

  The content (% by weight) of the polyol (PL) in (A) is preferably 40 to 65, more preferably 42 to 62, and most preferably 45, from the viewpoint of preventing aggregation of (JR) and mechanical properties of polyurethane. ~ 60.

The manufacturing method (A) includes the following manufacturing methods (1) and (2).
(1) A method for producing an ethylenically unsaturated compound (E) by polymerization in (PL).
(2) A method of producing (JR) by polymerizing the ethylenically unsaturated compound (E) and then dispersing (JR) in (PL).

The production method (1) is a method of polymerizing the ethylenically unsaturated compound (E) in a dispersion medium composed of polyol (PL).
Examples of the polymerization method include radical polymerization, coordination anion polymerization, metathesis polymerization, Diels-Alder polymerization, and the like. From an industrial viewpoint, radical polymerization is preferable.

  As the radical polymerization method, various methods, for example, a method of polymerizing (E) in the presence of the radical polymerization initiator (K) in (PL) containing the dispersant (B) (for example, US Pat. No. 3,383,351) Can be used.

  As (K), compounds that generate free radicals and initiate polymerization, such as azo compounds and peroxides (for example, those described in JP-A No. 2005-162791, etc.) can be used. The 10-hour half-life temperature of (K) is preferably 30 to 150 ° C., more preferably 40 to 140 ° C., and particularly preferably 50 to 130 ° C. from the viewpoint of the polymerization rate and productivity of (E).

  The use amount (% by weight) of (K) is preferably 0.05 to 20, more preferably 0.1 to 0.1, based on the weight of (E) from the viewpoint of the polymerization rate of (E) and the mechanical properties of polyurethane. 5, particularly preferably 0.2-2.

As the dispersant (B), various dispersants having Mn of 1,000 or more (preferably 1,100 to 10,000 from the viewpoint of dispersibility), for example, known dispersants used in the production of polymer polyols (for example, JP, 2005-162791, A) etc. can be used, and (B) includes a reactive dispersant having an ethylenically unsaturated group that can be copolymerized with St or ACN, and St or Non-reactive dispersants that do not copolymerize with ACN are included.
In the present invention, the reactive dispersant having an ethylenically unsaturated group is Mn 1,000 or more, and is distinguished from the other ethylenically unsaturated monomers (e) having Mn of less than 1,000.

As a specific example of (B),
[1] Macromer-type reactive dispersant obtained by reacting polyol (PL) with an ethylenically unsaturated compound Modified polyether polyol having an ethylenically unsaturated group (for example, those described in JP-A-08-333508), etc. ;
[2] Graft type non-reactive dispersant (PL) in which a polyol and an oligomer are combined. The difference in solubility parameter is 1.0 or less, and (PL) two or more affinity segments are side chains, (E) A graft type polymer (for example, described in JP-A-05-059134) having a polymer particle (JR) affinity segment having a solubility parameter difference of 2.0 or less as a main chain;
[3] Modification in which high molecular weight polyol type non-reactive dispersant (PL) is converted to high molecular weight (average molecular weight 1000 to 60,000) by reacting at least part of hydroxyl groups with methylene dihalide and / or ethylene dihalide Polyols (for example, those described in JP-A-07-196749) and the like;
[4] Oligomer type reactive dispersant 1,000 to 30,000 weight average molecular weight (hereinafter abbreviated as Mw) [measurement is by gel permeation chromatography (GPC) method. And at least a part of the vinyl oligomer that is soluble in (PL), and a dispersant comprising a combination of the oligomer and a vinyl group-containing modified polyol obtained by reacting the modified polyol having a high molecular weight described in [3]. (For example, those described in JP 09-77968 A) and the like;
[5] A nitrogen-containing bond-containing unsaturated polyol obtained by bonding (PL) and a monovalent active hydrogen-containing compound having at least one ethylenically unsaturated group via a polyisocyanate (for example, JP 2002-308920 A). And the like, and the like.
Of these, [1], [4] and [5] are more preferable from the viewpoint of the particle diameter of (JR), and [5] is more preferable.

  The use amount (% by weight) of (B) is preferably 2 to 20 and more preferably 5 to 15 from the viewpoint of the particle diameter of (JR) and the viscosity of the polymer polyol, based on the weight of (PL).

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

In radical polymerization, a chain transfer agent (G) may be used if necessary. As (G), various chain transfer agents (for example, those described in JP-A-2005-162791, etc.) such as aliphatic thiols (C1-20, such as n-dodecanethiol, mercaptoethanol) can be used.
The use amount (% by weight) of (G) is preferably 0.01 to 2, more preferably 0.1 to 1, from the viewpoint of the viscosity of (A) and the mechanical properties of polyurethane based on the weight of (E). It is.

The production method of the polymer polyol includes various production methods such as a batch polymerization method and a continuous polymerization method (for example, those described in JP-A Nos. 2005-162791 and 8-333508). Batch polymerization methods include batch polymerization methods, drop polymerization methods, multistage batch polymerization methods and the like; continuous polymerization methods include multistage continuous polymerization methods and the like.
The production method for obtaining the polymer polyol (A) of the present invention is preferably a batch polymerization method and a continuous polymerization method, and more preferably a multistage batch polymerization method and a multistage continuous polymerization method from the viewpoint of productivity and particle diameter.
The multistage batch polymerization method is a batch polymerization method including n times (n is an integer of 2 or more) polymerization steps, and includes the following steps (I) to (III). In the production method, the steps (I) to (III) may be carried out in this order, and the reaction vessel in which each step is carried out may be the same or different.
Step (I): Ethylenically unsaturated compound (E), polyol (PL) and, if necessary, dispersing agent (B) and diluting solvent (C) are added, and radical polymerization initiator (K) is added for polymerization. And obtaining a base polymer polyol (BA ₁ ).
Step (II): (E) is added to the obtained (BA _i-1 ), and (PL), (B) and (C) are further added as necessary, and then (K) is added to polymerize the base. A step of obtaining a polymer polyol (BA _i ) [i is an integer of 2 to (n-1)]. The step (II) is not performed when n is 2, and is performed (n-2) times when n is 3 or more. At the end of the step (II), the base polymer polyol (BA _n-1 )
Step (III): (E) is added to the obtained (BA _n-1 ), and (PL), (B), and (C) are added as necessary, and then (K) is added to polymerize the polymer polyol ( A) obtaining step.
n (the number of polymerization stages) is the number of processes for performing polymerization, and is the total number of polymerization processes in the above-mentioned processes (I), (II) and (III).
n is preferably 2 to 7, more preferably 2 to 5, and particularly preferably 3 to 4, from the viewpoint of reducing the coarse particle content and productivity.

  The radical polymerization initiator (K) may be used as it is, or may be used after being dissolved (or dispersed) in the diluent solvent (C), the dispersant (B) and / or the polyol (PL).

Among the production methods (1) and (2) of the polymer polyol (A), the production method (2) comprises producing polymer particles (JR), and then dispersing (JR) in the polyol (PL). This is a method for obtaining a polymer polyol, and examples thereof include the following methods.
First, a dispersion is produced by emulsion polymerization or suspension polymerization of an ethylenically unsaturated compound by various methods (for example, methods described in JP-A-5-148328 and JP-A-8-100006). To do. If necessary, the obtained (JR) dispersion is classified using a wet classifier (precipitation tank system, mechanical classifier system, centrifugal classifier system, etc.). The polymer polyol (A) of the present invention can be obtained by dispersing (JR) thus obtained in (PL).
In dispersing, the (JR) dispersion obtained by polymerization or subsequent wet classification and classification may be used as it is, or after the dispersion medium is distilled off from the (JR) dispersion. When the (JR) dispersion is used as it is, the polymer polyol of the present invention is obtained by mixing the (JR) dispersion and the polyol (PL) and then distilling off the dispersion medium.
Also, when used after distilling off the dispersion medium from the (JR) dispersion, when (JR) is dispersed in (PL), if it is dispersed by applying high shear, aggregation of (JR) can be easily prevented. it can. As an apparatus used for the dispersion, a dispersion apparatus capable of applying a high share such as a homomixer is preferable.

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

  The polymer polyol (A) of the present invention can be used as a polyol used for the production of polyurethane (polyurethane elastomer, polyurethane foam, etc.). That is, (A) or a polyol component (Po) containing (A) and an isocyanate component (Is) composed of a polyisocyanate [hereinafter, a composition composed of (Po) and (Is) is referred to as a polyurethane-forming composition. is there. ] Can be reacted by a known method (for example, the method described in JP-A No. 2004-263192) or the like to obtain a polyurethane.

As the polyol component (Po), in addition to (A) of the present invention, a polyol and a known polymer polyol other than (A) are used as a raw material when producing polyurethane as long as the effects of the present invention are not impaired. May be.
As the polyol, the above-described polyol (PL) or the like can be used, and as the known polymer polyol, for example, a polymer polyol described in JP-A-2005-162791 can be used.
Although the usage-amount (weight%) of a polyol can be suitably adjusted from a viewpoint of the mechanical physical property of a polyurethane based on the weight of (A), Preferably it is 1-1000.
The use amount (% by weight) of a known polymer polyol other than (A) is preferably based on the weight of (A) from the viewpoint of reducing the mechanical properties of polyurethane and clogging of strainers and discharge ports of polyurethane production equipment. 1-100.

  The amount (% by weight) of (A) used in the polyol component (Po) is preferably 10 to 100, more preferably from the viewpoint of the mechanical properties of the resulting polyurethane and the viscosity of the polyol component, based on the weight of (Po). Is 15 to 90, particularly preferably 20 to 80, and most preferably 25 to 70.

As the isocyanate component (Is), known polyisocyanates (for example, those described in JP-A No. 2005-162791) and the like conventionally used in the production of polyurethane can be used.
Among these, 2,4- and 2,6-tolylene diisocyanate (TDI), a mixture of these isomers, and crude TDI (residue when TDI is purified) are preferable from the viewpoint of mechanical properties of polyurethane. 4,4'- and 2,4'-diphenylmethane diisocyanate (MDI), mixtures of these isomers, crude MDI (residue when MDI is purified); and urethane groups derived from these polyisocyanates , A modified polyisocyanate containing a carbodiimide group, an allophanate group, a urea group, a burette group or an isocyanurate group.

  The NCO index [equivalent ratio of NCO group and active hydrogen atom (NCO group / active hydrogen atom) × 100] in the production of polyurethane can be appropriately adjusted from the viewpoint of the mechanical properties of polyurethane, but preferably 80 to 140. More preferably, it is 85-120, Most preferably, it is 95-115.

  In order to promote the reaction in the production of polyurethane, various catalysts (for example, those described in JP-A-2005-162791) used in the urethanization reaction can be contained in the polyurethane-forming composition. The amount (% by weight) of the catalyst used is usually 10 or less, preferably 0.001 to 5, based on the total weight of the polyurethane-forming composition.

In the production of polyurethane, various foaming agents (for example, those described in JP-A-2006-152188) [water, HFC (hydrofluorocarbon), HCFC (hydrochlorofluorocarbon), methylene chloride, etc.] are added to a polyurethane-forming composition. It can be made to contain in a thing and can be set as a polyurethane foam. The amount (% by weight) of the foaming agent can be changed depending on the desired density of the polyurethane foam, and is not particularly limited, but is usually 20 or less based on the total weight of the polyurethane-forming composition.
When producing a polyurethane foam, if necessary, a foam stabilizer can be further contained in the polyurethane-forming composition. As the foam stabilizer, various foam stabilizers (for example, those described in JP-A No. 2005-162791) can be used. From the viewpoint of uniformity of cell diameter in the polyurethane foam, a silicone surfactant (for example, polysiloxane) is preferable. Siloxane-polyoxyalkylene copolymer).
The amount (% by weight) of the foam stabilizer used is usually 5 or less, preferably 0.01 to 2, based on the total weight of the polyurethane-forming composition.

In the production of polyurethane, a flame retardant can be further contained in the polyurethane-forming composition as necessary. Examples of the flame retardant include those described in JP-A-2005-162791, such as melamine, phosphate ester, halogenated phosphate ester, and phosphazene.
The amount (% by weight) of the flame retardant used is usually 30 or less, preferably 0.01 to 10, based on the total weight of the polyurethane-forming composition.

  In the production of polyurethane, a reaction retarder, a colorant, an internal mold release agent, an anti-aging agent, an anti-oxidant, a plasticizer, a disinfectant, and a filler (carbon black) as long as the effects of the present invention are not impaired. The polyurethane-forming composition may contain at least one other additive selected from the group consisting of:

The polyurethane can be produced by various methods (for example, the method described in JP-A-2005-162791), and examples thereof include a one-shot method, a semi-prepolymer method, and a prepolymer method.
For the production of polyurethane, a conventionally used production apparatus (such as a low-pressure or high-pressure machine) can be used. In the case of no solvent, an apparatus such as a kneader or an extruder can be used. Further, when producing non-foamed or foamed polyurethane, a closed mold or an open mold can be used.

  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 description, “%”, “part” and “ratio” respectively represent “% by weight”, “part by weight” and “weight ratio” unless otherwise specified.

The composition, symbols, etc. of the raw materials used in the examples and comparative examples are as follows.
(1) Polyol Polyol (PL-1): Polyol polyol having a hydroxyl value of 56, an internal EO unit content of 5%, and a primary hydroxyl group ratio of 2 mol%, in which glycerin is block-added in the order of PO-EO-PO. PL-2): A polyol having a hydroxyl value of 32, a terminal EO unit content of 12%, and a primary hydroxyl group ratio of 80 mol%, which is block-added in the order of PO-EO to pentaerythritol Polyol (PL-3): JP Polyol {(PL-3) of a hydroxyl group = 56, internal EO unit content = 0%, primary hydroxyl group ratio 74%, in which PO is added to glycerin produced according to 2000-344881 % Corresponds to polyol (PL1) having primary hydroxyl group-containing molecular ends}
Polyol (PL-4): PO added to glycerin produced according to Japanese Patent No. 3934493, followed by addition of EO, hydroxyl value = 56.5, terminal EO unit content = 16.7%, 1 Polyol having a ratio of secondary hydroxyl group of 90% (2) Radical polymerization initiator K-1: 2,2′-azobis (2,4-dimethylvaleronitrile) [trade name “V-65”, Wako Pure Chemical Industries, Ltd. Made)
K-2: 1,1′-azobis (2-methylbutyronitrile) [trade name “V-59”, manufactured by Wako Pure Chemical Industries, Ltd.]
K-3: 1,1-azobis (cyclohexane-1-carbonitrile) [trade name “V-40”, manufactured by Wako Pure Chemical Industries, Ltd.]
K-4: Dicumyl peroxide [trade name “Park Mill D”, manufactured by NOF Corporation]
(3) Dispersant B-1: hydroxyl value = 20, number of unsaturated groups / obtained by joining 0.14 mol of polyol (PL-2) and 0.07 mol of 2-hydroxyethyl methacrylate with 0.16 mol of TDI Reactive dispersant having a nitrogen-containing group bond group number of 0.22 / 1 [as described in JP-A-2002-308920]
(4) Polyisocyanate TDI-80: trade name “Coronate T-80” [manufactured by Nippon Polyurethane Industry Co., Ltd.]
(5) Catalyst Catalyst A: Trade name “Neostan U-28” (stannous octylate) [manufactured by Nitto Kasei Co., Ltd.]
Catalyst B: Trade name “DABCO” (triethylenediamine) [manufactured by Nippon Emulsifier Co., Ltd.]
(6) Foam stabilizer Product name “SRX-280A” (polyether-modified dimethylpolysiloxane) [manufactured by Toray Dow Corning Silicone Co., Ltd.]

The measurement and evaluation methods in the examples are as follows.
<Content of polymer particles (JR): (PC)>
About 5 g of polymer polyol is precisely weighed in a 50 ml centrifuge tube for centrifugal separation made of SUS, and the weight is set to the weight of polymer polyol (W1). Dilute with 15 g of methanol. Using a cooling centrifuge [model number: GRX-220, manufactured by Tommy Seiko 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 15 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, the dried sediment is weighed, and the weight is defined as (W2). The value calculated by the following formula (2) is the polymer particle content (% by weight).

Polymer particle content (% by weight) = (W2) × 100 / (W1) (2)

<Polymerization rate>
The polymerization rate was calculated from the residual monomer content of each monomer with respect to the charged monomer amount. 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.

Polymerization rate [wt%]
= 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) / (weight of polymer polyol [g])
M = (peak area of internal standard) / (weight of internal standard [g])

The factor for the internal standard substance is obtained by dividing the peak area of each monomer when the weight is the same as the internal standard substance by the peak area of the internal standard substance.
Gas chromatograph measurement conditions (for styrene)
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)
Diluent: Dipropylene glycol monomethyl ether grade 1 [Wako Pure Chemical Industries, Ltd.]
Injection temperature: 200 ° C
Column temperature: 110 ° C
Temperature increase rate: 5 ° C / min
Column final temperature: 200 ° C
Sample injection volume: 1 μl

<Primary hydroxyl group ratio>
(Measuring method)
About 30 mg of a sample is weighed into a sample tube for ¹ H-NMR having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added, and the mixture is well shaken and allowed to stand at 25 ° C. for about 5 minutes to make the polyol a trifluoroacetic acid ester, which is used as a sample for analysis. This analytical sample is measured by ¹ H-NMR.
The deuterated solvent here is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.
(Calculation method of primary hydroxyl group ratio)
A signal derived from a methylene group with a primary hydroxyl group is observed at around 4.3 ppm, and a signal derived from a methine group with a secondary hydroxyl group is observed at around 5.2 ppm. The rate is calculated by the following formula.
Primary hydroxyl group ratio (mol%) = [r / (r + 2s)] × 100
r: integral value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm s: integral value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm

<Volume average particle diameter>
30 ml of methanol is put into a 50 ml glass beaker, 2 mg of polymer polyol is added, and the mixture is stirred and mixed with a magnetic stirrer at 400 rpm × 3 minutes using a stirrer piece having a major axis of 2 cm and a minor axis of 0.5 cm to obtain a uniform solution. After mixing, the sample is put into a measurement cell within 5 minutes, and the volume average particle size based on the volume is measured using a laser diffraction / scattering particle size distribution measuring device [model number: LA-750, manufactured by Horiba, Ltd.].

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

<Whiteness of polymer polyol>
The polymer polyol is measured using a color difference meter [manufactured by Konica Minolta Holdings, Inc.].

<Evaluation>
The whiteness of the polymer polyol and the physical properties of the polyurethane foam were evaluated and evaluated according to the following criteria.

☆ Whiteness is 3 or less, foam properties are good ◎ Whiteness is greater than 3 and 4.5 or less, foam properties are good ○ Whiteness is greater than 4.5 and 5.5 or less, foam properties are good Δ Whiteness is larger than 5.5 and 6.0 or less, foam physical properties are good × Whiteness is larger than 6.0, or foam physical properties are poor

Example 1 [Production of polymer polyol (A-1)]
[Step I] In a pressure-resistant reaction vessel made of SUS at 25 ° C., 406 parts of polyol (PL-1), 29 parts of polyol (PL-3), 35 parts of ACN, 84 parts of St, allyl alcohol PO 2.2 mol adduct 6 parts, 0.36 part of divinylbenzene, 44.2 parts of dispersant (B-1) and 32 parts of xylene were added, and the temperature was adjusted to 100 ° C. with stirring. A solution prepared by dissolving 1.19 parts of radical polymerization initiator (K-1), 0.36 parts of (K-2) and 0.12 parts of (K-3) in 8 parts of xylene was charged in 5 seconds. Mix and start the polymerization. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA1-1).
[Step II] Subsequently, in a reaction vessel at 25 ° C., 37 parts of polyol (PL-1), 3 parts of polyol (PL-3), 45 parts of ACN, 108 parts of St, 8.5 mol of allyl alcohol PO adduct 8.5 And 0.46 part of divinylbenzene were added, and the temperature was adjusted to 95 ° C. with stirring. A solution prepared by dissolving 1.53 parts of (K-1), 0.46 parts of (K-2) and 0.15 parts of (K-3) in 11 parts of xylene was charged in 5 seconds and mixed to polymerize. Was started. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA1-2).
[Step III] Subsequently, at 25 ° C., 50 parts of ACN, 120 parts of St, 8.5 parts of allyl alcohol PO 2.2 mol adduct and 0.51 part of divinylbenzene were placed in a reaction vessel, and the temperature was raised to 90 ° C. with stirring. It was adjusted. A solution prepared by dissolving 1.70 parts of (K-1), 0.51 part of (K-2), 0.17 part of (K-3) and 0.17 part of (K-4) in 13 parts of xylene. Was charged in 5 seconds and 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 about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA1-3). The polymer polyol (A-1) was obtained by stripping unreacted monomer and xylene from (BA1-3) at 2,666-3,999 Pa (20-30 torr) for 2 hours under reduced pressure. (A-1) was measured and evaluated by the above method. The results are shown in Table 1.

Example 2 [Production of polymer polyol (A-2)]
In Example 1, in Step I, instead of 406 parts of polyol (PL-1) and 29 parts of polyol (PL-3), 423 parts of polyol (PL-1) and 12 parts of polyol (PL-3), Example 1 except that, in Step II, instead of 37 parts of polyol (PL-1) and 3 parts of polyol (PL-3), 39 parts of polyol (PL-1) and 1 part of polyol (PL-3) were used. In the same manner as above, a polymer polyol (A-2) was obtained. (A-2) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 [Production of polymer polyol (A-3)]
In Example 1, in Step I, instead of 406 parts of polyol (PL-1) and polyol (PL-3) 29, 391 parts of polyol (PL-1) and 44 parts of polyol (PL-3), II Example 1 with the exception that 36 parts of polyol (PL-1) and 4 parts of polyol (PL-3) were used instead of 37 parts of polyol (PL-1) and 3 parts of polyol (PL-3) in the process. Similarly, polymer polyol (A-3) was obtained. (A-3) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4 [Production of polymer polyol (A-4)]
[Step I] In a pressure resistant reaction vessel made of SUS, at 25 ° C., 409 parts of polyol (PL-1), 26 parts of polyol (PL-3), 48.2 parts of ACN, 77.4 parts of Styl alcohol, 2.2 mol of allyl alcohol PO 7.6 parts of adduct, 0.38 part of divinylbenzene, 44.2 parts of dispersant (B-1) and 35.7 parts of xylene were added, and the temperature was adjusted to 100 ° C. with stirring. A solution prepared by dissolving 1.26 parts of radical polymerization initiator (K-1), 0.38 parts of (K-2) and 0.13 parts of (K-3) in 8.8 parts of xylene was added for 5 seconds. Charged and mixed to initiate polymerization. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA4-1).
[Step II] Subsequently, in a reaction vessel at 25 ° C., 38 parts of polyol (PL-1), 2.0 parts of polyol (PL-3), 58.2 parts of ACN, St93.5 parts, allyl alcohol PO2.2. Mole adduct 8.2 parts and 0.46 part of divinylbenzene were added, and the temperature was adjusted to 95 ° C. with stirring. A solution prepared by dissolving 1.62 parts of (K-1), 0.46 parts of (K-2), and 0.15 parts of (K-3) in 10.6 parts of xylene was charged in 5 seconds. Then, polymerization was started. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA4-2).
[Step III] A continuous polymerization apparatus (SUS pressure-resistant reaction vessel connected with a liquid feed line and an overflow line) was prepared, and the polymer polyol (BA4-2) 2,400 prepared in Step II in advance in the reaction vessel. The temperature was raised to 130 ° C. Next, 872.1 parts of (BA4-2), 63.2 parts of ACN, St101.5 parts, 8.2 parts of allyl alcohol PO 2.2 mol adduct, 0.49 parts of divinylbenzene, 8 parts of xylene, radical polymerization initiator (K-2) 1.65 parts of the raw material mixture is line blended using a static mixer, and then merged with a part (Z) of an overflow reaction liquid described later at a rate of 100 parts / min. The solution was sent to On the other hand, the reaction liquid is overflowed from the polymerization tank at 2,100 parts / minute, and a part (Z) of the reaction liquid containing the overflowed polymer polyol is mixed with the raw material just before entering the reaction vessel while cooling to 130 ° C. The solution was merged at a rate of 2,000 parts / minute and sent to the polymerization tank. This operation was continuously performed and polymerized at 130 ° C. to obtain a polymer polyol intermediate (BA4-3). The polymer polyol (A-4) was obtained by stripping unreacted monomer and xylene from (BA4-3) at 2,666-3,999 Pa (20-30 torr) under reduced pressure for 2 hours. The polymer (A-4) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5 [Production of polymer polyol (A-5)]
In Example 1, in Step I, instead of 406 parts of polyol (PL-1) and 29.0 parts of polyol (PL-3), 391 parts of polyol (PL-1) and 44. 0 parts, except that in Step II, instead of 37 parts of polyol (PL-1) and 3 parts of polyol (PL-3), 36 parts of polyol (PL-1) and 4 parts of polyol (PL-3) were used. Produced polymer polyol (A-5) in the same manner as in Example 1. (A-5) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6 [Production of polymer polyol (A-6)]
[Step I] In a pressure resistant reaction vessel made of SUS at 25 ° C., 406 parts of polyol (PL-1), 29 parts of polyol (PL-3), 56.9 parts of ACN, St111.7 parts, 2.2 mol of allyl alcohol PO 7.9 parts of adduct, 0.51 part of divinylbenzene, 58.0 parts of dispersant (B-1) and 31.6 parts of xylene were added, and the temperature was adjusted to 100 ° C. with stirring. A solution prepared by dissolving 1.69 parts of radical polymerization initiator (K-1), 0.51 part of (K-2) and 0.17 part of (K-3) in 12 parts of xylene was charged in 5 seconds. Mix and start the polymerization. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA6-1).
[Step II] Subsequently, at 25 ° C., 37 parts of polyol (PL-1), 3 parts of polyol (PL-3), 66.9 parts of ACN, 131.3 parts of Styl alcohol, and 2.2 mol of allyl alcohol PO were added to the reaction vessel. 8.5 parts of the product and 0.59 parts of divinylbenzene were added, and the temperature was adjusted to 95 ° C. with stirring. A solution in which 1.98 parts of (K-1), 0.59 parts of (K-2) and 0.20 parts of (K-3) were dissolved in 13.9 parts of xylene was charged in 5 seconds. Then, polymerization was started. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA6-2).
[Step III] Subsequently, at 25 ° C., 71.9 parts of ACN, 141.1 parts of St, 8.5 parts of allyl alcohol PO 2.2 mol adduct and 0.64 parts of divinylbenzene were placed in a reaction vessel. The temperature was adjusted to 90 ° C. (K-1) 2.13 parts, (K-2) 0.64 parts, (K-3) 0.21 parts and (K-4) 0.21 parts dissolved in xylene 16 parts Was charged in 5 seconds and 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 about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BA6-3). The unreacted monomer and xylene were stripped from (BA6-3) at 2,666-3,999 Pa (20-30 torr) for 2 hours under reduced pressure to obtain a polymer polyol (A-6). (A-6) was evaluated by the measurement and evaluation methods described above. The results are shown in Table 1.

Example 7 [Production of polymer polyol (A-7)]
In Example 1, except that the number of parts of allyl alcohol PO2.2 mol adduct was 0 parts in Step I, Step II, and Step III, the polymer polyol (A-7) was prepared in the same manner as in Example 1. Got. (A-7) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 8 [Production of polymer polyol (A-8)]
[First Step] In a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet, 239 parts of polyol (PL-1), polyol (PL- 4) 57 parts, 57.4 parts of dispersant (B-1) and 124 parts of xylene were added, and after nitrogen substitution, the temperature was raised to 130 ° C. with stirring under a nitrogen atmosphere (until the end of polymerization). Subsequently, 142 parts of polyol (PL-1), 105 parts of ACN, 245 parts of styrene, 0.35 part of divinylbenzene, 40.3 parts of adduct of 2.2 mol of allyl alcohol PO, 17.5 parts of dispersant (B-1), (K-2) A monomer-containing mixed solution (Z1) prepared by previously mixing 3.50 parts and 10.5 parts of xylene was continuously added dropwise at a rate of 25 parts / minute using a dropping pump. Polymerization was carried out at 30 ° C. for 30 minutes. Furthermore, it cooled to 25 degreeC and obtained the polymer polyol intermediate body (BA8-1).
[Second Step] Prepare two tanks of continuous polymerization equipment (2L SUS pressure-resistant reaction vessel connected to the liquid feed line and overflow line), and connect the first tank overflow line to the inlet of the second tank. Place in series. Each of the first and second polymerization tanks was charged with 2000 parts of polyol (PL-1) in advance and heated to 130 ° C. Polymer polyol intermediate (BA8-1) 127.8 parts, polyol (PL-1) 196 parts, polyol (PL-4) 11 parts, ACN 29.0 parts, styrene 67.7 parts, divinylbenzene 1.21 parts, A raw material mixture (G1-1) obtained by mixing 6.8 parts of allyl alcohol PO 2.2 mol adduct, 29.0 parts of (B-1), 0.97 parts of (K-2) and 39.9 parts of xylene. After line blending using a static mixer, the solution was continuously fed to the first polymerization tank at a feeding speed of 113 parts / min, and overflowed from the polymerization tank to obtain a polymer polyol intermediate (BA8-2). . The polymer polyol intermediate (BA8-2) overflowed from the first polymerization tank was continuously fed to the second polymerization tank at a feeding rate of 113 parts / minute.
[Third step] Polymer polyol intermediate (BA8-2) and 112 parts of polyol (PL-1), polyol (PL-4) overflowed from the first polymerization tank at a rate of 113 parts / min. ) After line blending 6 parts, ACN 91.8 parts, styrene 214 parts, (K-2) 3.06 parts and xylene 9.2 parts using a static mixer, The polymer polyol intermediate was continuously fed to the second polymerization tank at a rate of 96.9 parts / minute, and the reaction liquid overflowed from the polymerization tank was stocked in a SUS receiving tank. (BA8-3) was obtained. The polymer polyol (A-8) was obtained by stripping unreacted monomer and xylene from (BA8-3) at 2,666-3,999 Pa (20-30 torr) for 2 hours at 130-140 ° C. under reduced pressure. . (A-8) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 [Production of polymer polyol (R-1)]
[Step I] In a SUS pressure-resistant reaction vessel at 25 ° C., 316 parts polyol (PL-1), 4 parts polyol (PL-3), 45.0 parts ACN, 108.7 parts St, 0.46 parts divinylbenzene Then, 54.4 parts of dispersant (B-1) and 22.7 parts of xylene were added, and the temperature was adjusted to 100 ° C. with stirring. A solution prepared by dissolving 1.53 parts of radical polymerization initiator (K-1), 0.46 parts of (K-2) and 0.15 parts of (K-3) in 11 parts of xylene was charged in 5 seconds. Mix and start the polymerization. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BAR1-1).
[Step II] Subsequently, at 25 ° C., 39 parts of polyol (PL-1), 1 part of polyol (PL-3), 55.0 parts of ACN, 131.9 parts of St and 0.56 parts of divinylbenzene were added to the reaction vessel. The temperature was adjusted to 95 ° C. with stirring. A solution prepared by dissolving 1.87 parts of (K-1), 0.56 parts of (K-2), and 0.19 parts of (K-3) in 13.1 parts of xylene is charged and mixed for 5 seconds. Then, polymerization was started. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BAR1-2).
[Step III] Subsequently, 60.0 parts of ACN, 143.9 parts of StN, and 0.61 part of divinylbenzene were placed in a reaction vessel at 25 ° C., and the temperature was adjusted to 90 ° C. with stirring. Here, 2.04 parts of (K-1), 0.61 part of (K-2), 0.20 part of (K-3) and 0.20 part of (K-4) were dissolved in 15.3 parts of xylene. The liquid was charged for 5 seconds and 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 about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BAR1-3). The unreacted monomer and xylene were stripped from (BAR1-3) at 2,666-3,999 Pa (20-30 torr) for 2 hours under reduced pressure to obtain a polymer polyol (R-1). (R-1) was evaluated by the above measurement and evaluation methods. The results are shown in Table 1.

Comparative Example 2 [Production of polymer polyol (R-2)]
[Step I] In a pressure resistant reaction vessel made of SUS at 25 ° C., 377 parts of polyol (PL-1), 73.0 parts of polyol (PL-3), 100.0 parts of ACN, St34.6 parts, allyl alcohol PO2. 7.4 parts of 2-mole adduct, 0.40 part of divinylbenzene, 43.8 parts of dispersant (B-1) and 32.5 parts of xylene were added, and the temperature was adjusted to 100 ° C. with stirring. A solution prepared by dissolving 1.35 parts of radical polymerization initiator (K-1), 0.40 part of (K-2) and 0.13 part of (K-3) in 9 parts of xylene was charged in 5 seconds. Mix and start the polymerization. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BAR2-1).
[Step II] Subsequently, 34 parts of polyol (PL-1), 6 parts of polyol (PL-3), 110.0 parts of ACN, 38.1 parts of St, and 2.2 mol of allyl alcohol PO were added to the reaction vessel at 25 ° C. 7.7 parts of the product and 0.44 part of divinylbenzene were added, and the temperature was adjusted to 95 ° C. with stirring. Here, a solution prepared by dissolving 1.48 parts of (K-1), 0.44 parts of (K-2) and 0.15 parts of (K-3) in 10.4 parts of xylene was charged in 5 seconds and mixed. Then, polymerization was started. After adding the radical polymerization initiator solution, the polymerization reaction started rapidly within 1 minute, and reached the maximum temperature of about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BAR2-2).
[Step III] Subsequently, at 25 ° C., 115.0 parts of ACN, 39.8 parts of St, 7.7 parts of allyl alcohol PO2.2 mol adduct and 0.46 parts of divinylbenzene were placed in a reaction vessel, and the mixture was stirred. The temperature was adjusted to 90 ° C. Here, 1.55 parts of (K-1), 0.46 parts of (K-2), 0.15 parts of (K-3) and 0.15 parts of (K-4) were dissolved in 11.6 parts of xylene. The liquid was charged for 5 seconds and 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 about 160 ° C. in about 6 minutes. After reaching this temperature, the mixture was aged at 150 to 170 ° C. for about 10 minutes and then cooled to 25 ° C. to obtain a polymer polyol intermediate (BAR2-3). The unreacted monomer and xylene were stripped from (BAR2-3) at 2,666-3,999 Pa (20-30 torr) for 2 hours under reduced pressure to obtain a polymer polyol (R-2). (R-2) was measured and evaluated by the method described above. The results are shown in Table 1.

Comparative Example 3 [Production of polymer polyol (R-3)]
The polymer polyol (R-3) was obtained by stripping unreacted monomer and xylene from (H-1) obtained in Step I of Example 1 under reduced pressure in the same manner as in Example 1. . (R-3) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 [Production of polymer polyol (R-4)]
In Example 1, instead of 413 parts of polyol (PL-1) and 22 parts of polyol (PL-3) in Step I, 435 parts of polyol (PL-1) and polyol (PL-1) in Step II A polymer polyol (R-4) was obtained in the same manner as in Example 1 except that 40 parts of polyol (PL-1) was used instead of 38 parts and 2 parts of polyol (PL-3). (R-4) was measured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 9 to 16 and Comparative Examples 5 to 8 [Production of polyurethane foam]
Using the polymer polyols (A-1 to A-8) obtained in Examples 1 to 8 and the comparative polymer polyols (R-1 to R-4) obtained in Comparative Examples 1 to 4, Table 2 Polyurethane foam was manufactured by the foaming formulation shown below with a blending ratio of The physical properties of these foams were evaluated by the following methods. The results are shown in Table 2.
<Foaming prescription>
[1] The temperature of each of the polymer polyol, polyol (PL-1) and polyisocyanate was adjusted to 25 ± 2 ° C.
[2] Polymer polyol, polyol (PL-1), foam stabilizer, water, and catalyst were charged in a 1L stainless steel beaker and stirred and mixed at 25 ° C ± 2 ° C. The mixture was stirred using [Homodisper, manufactured by Tokushu Kika 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.

<Method for evaluating physical properties of foam>
(1) Density (kg / m ³ ): Conforms to JIS K6400-1997 [Item 5].
(2) 25% ILD (hardness) (kgf / 314 cm ² ): Conforms to JIS K6382-1995 [Item 5.3].
(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) Cut elongation (%): compliant with JIS K6301-1995 [Item 3] (6) Compression set (%) : Conforms to JIS K6382-1995 [Item 5.5].
(7) Breathability (cc / cm ² / s): Conforms to JIS K6400-7: 2004.

From the results of Table 1 and Table 2, the polymer polyol of Comparative Example 1 has the same proportion of primary hydroxyl groups as the polymer polyols of Examples 1 to 8, but the PL1 content is low and the foam physical properties are reduced. I understand that. In particular, it can be seen that the 25% ILD value representing the foam hardness and the breathability value are extremely low. Further, with respect to the polymer polyol of Comparative Example 2, since the ratio of primary hydroxyl groups and the PL1 content were high, shrinkage was caused after foaming, making it impossible to measure foam properties. In addition, since the polymer polyol of the comparative example 2 has much content of ACN, the whiteness of a polymer polyol is very bad. Further, the polymer polyol of Comparative Example 3 has a low polymer particle content, a value of 25% ILD representing foam hardness among the foam physical properties is extremely low, and the ratio of primary hydroxyl groups is also high. Of the physical properties, the value of air permeability is low. Since the polymer polyol of Comparative Example 4 has a low PL1 content and a low ratio of primary hydroxyl groups, the 25% ILD value of the foam properties is extremely low.
In general, the physical properties of polyurethane foam indicate that 25% ILD, tensile strength, tear strength, cut elongation and air permeability are better as the numerical value is larger, and compression set is smaller as the numerical value is smaller.

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

Claims (6)

In the polymer polyol in which the polymer particles (JR) containing the ethylenically unsaturated compound (E) as a structural unit are contained in the polyol (PL), the molecular terminal primary hydroxyl group based on the molecular terminal hydroxyl group in (PL) The ratio of the polyol (PL1) having a primary hydroxyl group-containing molecular terminal represented by the following general formula (1) based on the weight of (PL) is 2 to 10% based on the weight of (PL). A polymer polyol (A),
[Wherein, R represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom. ] The polymer polyol according to claim 1, wherein the content of the polymer particles (JR) is 40 to 60% based on the weight of the polymer polyol (A). The polymer polyol (A) according to claim 1 or 2, wherein the ethylenically unsaturated compound (E) contains 0.1 to 40% by weight of acrylonitrile based on the weight of (E). The ethylenically unsaturated compound (E) contains 0.1 to 10% by weight of an unsaturated alcohol (3 to 24 carbon atoms) alkylene (2 to 8 carbon atoms of an alkylene group) oxide adduct. Item 4. The polymer polyol according to any one of Items 1 to 3. In the manufacturing method of the polyurethane which consists of making a polyol component and an isocyanate component react, a polyol component contains 10-100 weight% of polymer polyols in any one of Claims 1-4 based on the weight of a polyol component. A process for producing polyurethane characterized by the above. The polyurethane formed from the polyol component and isocyanate component which contain 10-100 weight% of polymer polyols in any one of Claims 1-4 based on the weight of a polyol component.