JP2010084013A - Polymer polyol and method for producing polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that a polyurethane resin comprised of conventional polymer polyols is limited in making density lower while maintaining enough mechanical strength required for a cushion material for vehicle seats. <P>SOLUTION: The polymer polyol comprises including a polymer particle in the polyol (PL), wherein a primary hydroxylation ratio of the (PL), i.e. the ratio of primary OH attributed to molecular terminal hydroxyl group of the (PL) is 70-100 mol%, the (PL) contains 0.1-20 wt.% of oxyethylene unit based on the weight of the (PL), and the (PL) is a polyether polyol formed by random- and/or block-addition reaction of an alkylene oxide, mainly comprised of 1,2-alkylene oxide of not less than two carbon number, with an activated hydrogen so as to satisfy equations (1) and (2) when an average molar number of added ethylene oxide per one active hydrogen is x, primary hydroxylation ratio is y, and when x and y<10 equation (1): y≥42x<SP>0.47</SP>(1-x/41) (1) is satisfied, and, when x and y=10-20 equation (2): y≥0.328x+90.44 (2) is satisfied. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer polyol and a polyurethane resin. More specifically, the present invention relates to a polymer polyol which is suitable as a raw material for cushions for vehicle seats and the like, which has excellent reactivity with isocyanate and imparts excellent mechanical properties to polyurethane resin, and a method for producing polyurethane resin using the same.

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

  However, the conventional polyurethane resin using the above polymer polyol has a limit in maintaining the mechanical strength required as a cushion material for a vehicle seat and lowering the density.

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) having an ethylenically unsaturated compound (E) as a structural unit are contained in a polyol (PL), a primary class based on the molecular terminal hydroxyl group of (PL). The OH conversion rate is 70 to 100 mol%, the content of oxyethylene units in (PL) is 0.1 to 20 wt% based on the weight of (PL), and (PL) per active hydrogen When the average addition mole number x of the ethylene oxide is primary OH conversion rate y and x is less than 10, the following formula (1) is satisfied, and when it is 10 to 20, the relationship of the following formula (2) is satisfied. , A polymer polyol (A) which is a polyether polyol in which an alkylene oxide mainly composed of 2-alkylene oxide is randomly and / or block-added to activated hydrogen;
y ≧ 42x ^0.47 (1-x / 41) (1)
y ≧ 0.328x + 90.44 (2)
In addition, in the method for producing a polyurethane resin by reacting a polyol component and an isocyanate component, the polyol component is a method for producing a polyurethane resin containing 10 to 100% by weight of the polymer polyol based on the weight of the polyol component.

The method for producing a polymer polyol (A) of the present invention and a polyurethane resin using the polymer polyol has the following effects.
(1) The polyurethane resin produced using the polymer polyol of the present invention is excellent in mechanical strength.
(2) Since the polyurethane resin produced using the polymer polyol of the present invention is excellent in mechanical strength, the mechanical strength required as a cushion material for vehicle seats is maintained even if a low-density polyurethane resin is molded. be able to.

  The polymer polyol in the present invention is one in which polymer fine particles (JR) having an ethylenically unsaturated compound (E) as a structural unit are contained in the polyol (PL). As the ethylenically unsaturated compound (E), styrene (hereinafter abbreviated as St), acrylonitrile (hereinafter abbreviated as ACN), other ethylenically unsaturated monomers (e), and the like can be used.

  The proportion (% by weight) of ACN based on the weight of (E) constituting (JR) is preferably 40 to 97, more preferably 55 to 90, from the viewpoint of reducing the content of coarse particles and coloring the polymer polyol. More preferably, it is 60-80.

  The proportion (% by weight) of St based on the weight of (E) constituting (JR) is preferably 60 or less, more preferably 6 to 45, and most preferably 6 to 45, from the viewpoint of color reduction of the polymer polyol and the content of coarse particles. Preferably it is 15-40.

  The weight ratio of ACN to St (ACN: St) is preferably 97: 0 to 40:60, more preferably 90: 6 to 55:45, and most preferably 90: 6 to 55:45, from the viewpoint of the content of coarse particles and the reduction in coloration of the polymer polyol. Preferably it is 80: 15-60: 40.

  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), other ethylenically unsaturated monomer (e4)], polyfunctional (bifunctional or higher) monomer (e5), and the like can be used. These may be used alone or in combination of two or more.

(E1) includes C4-10, such as methacrylonitrile.
Examples of (e2) include C8-14, such as α-methylstyrene, hydroxystyrene, and chlorostyrene.
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; hydroxypolyoxyalkylene (alkylene group is C2-8) mono (meth) acrylate.
The (meth) acrylate means 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.

  Other ethylenically unsaturated monomers (e4) 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 (e5), 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.

  Of (e1) to (e5), (e3) and (e5) are preferable from the viewpoint of the viscosity of the polymer polyol and the physical properties of the polyurethane resin.

  The proportion (% by weight) of the other ethylenically unsaturated monomer (e) based on the weight of (E) constituting (JR) is preferably 60 or less, and the viscosity of the polymer polyol, dispersion stability, and physical properties of the polyurethane From the viewpoint, it is more preferably 0.01 to 30, then more preferably 0.05 to 20, particularly preferably 0.1 to 15, and most preferably 0.2 to 10.

  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 the polyurethane resin.

  The median (μm) of (JR) is preferably from 0.1 to 0.55, more preferably from 0.2 to 0.5, particularly preferably from 0.3 to 0, from the viewpoint of the viscosity of the polymer polyol and the properties of the polyurethane resin. .47. The median diameter is a particle diameter corresponding to 50% of the volume frequency, and the volume of the particle size distribution when the range of 0.040 to 262 μm measured by a laser diffraction / scattering particle size distribution measuring device is divided into 65 parts. It is by standard.

The polyol (PL) in the present invention includes a polyol (PL1) having a primary hydroxyl group-containing molecular terminal represented by the following general formula (1) and other polyols (PL2).
(PL1) is an AO adduct of an active hydrogen-containing compound, which 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).

In the formula, R represents a C1-10 hydrocarbon group which may be substituted with a halogen atom.
Specific examples of R in the general 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, bromoethyl groups, etc.), halogen atom-substituted phenyl groups (p-chloro- and p-bromophenyl groups, etc.), and these two types The above combination is mentioned.

The active hydrogen-containing compound is the same as the active hydrogen-containing compound described later.
C3- or higher 1,2-AO includes C3-12 or higher 1,2-AO among the aforementioned AOs. Specific examples include propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, C5-12 α-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.) and the like. Of these, PO, 1,2-butylene oxide, C5-12 α-olefin oxide, styrene oxide, and epichlorohydrin are preferable from the viewpoint of the viscosity of the polymer polyol and the mechanical properties of the polyurethane resin, and more preferably PO, 1,2-butylene oxide, C5-12 α-olefin oxide, particularly preferably PO, 1,2-butylene oxide, most preferably PO.

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

(PL1) can be produced by adding 1,2-AO to an active hydrogen-containing compound in the presence of a specific catalyst (α).
Examples of (α) include those described in Japanese Patent Application Laid-Open No. 2000-344881, and specifically, boron or aluminum compounds to which fluorine atoms, (substituted) phenyl groups and / or tertiary alkyl groups are bonded. For example, for boron compounds, triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, Examples include phenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris (pentafluorophenyl) aluminum, and bis (pentafluorophenyl) -t-butylaluminum.
Of these, triphenylborane, tris (pentafluorophenyl) borane, triphenylaluminum, and tris (pentafluorophenyl) aluminum are preferable, and tris (pentafluorophenyl) aluminum is more preferable from the viewpoint of the generation of primary hydroxyl group-containing molecular ends and the reaction rate of AO addition. (Pentafluorophenyl) -borane and -aluminum.
The conditions for addition of AO may be the same as those described in the above publications, 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 resin are produced. Preferably, 0.001-1% of the above-mentioned catalyst is used from the viewpoint of the reactivity during the reaction, and the reaction is usually performed at 0-250 ° C., preferably from 20-180 ° C. from the viewpoint of the reaction rate of AO addition and the mechanical properties of the polyurethane resin. Can be done.

By adding ethylene oxide (hereinafter abbreviated as EO) to the above 1,2-AO adduct, a polyol having a higher primary OH conversion rate can be obtained, and this can also be used as (PL1). it can. The use of this polyol is because the primary OH conversion rate of the polyol before EO addition is usually as large as 40% or more, preferably 60% or more, and more preferably 70% or more. The OH conversion rate can be increased, and it is preferable that x and y of the polyol (PL) satisfy the relationship described later. In addition, the catalyst used for the EO addition may use the boron or aluminum compound as it is, or may use another catalyst that is usually used instead.
Other catalysts include basic catalysts such as sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium carbonate and triethylenediamine; acid catalysts such as boron trifluoride, tin chloride, triethylaluminum and heteropolyacid; zinc hexacyano Cobaltate; phosphazene compounds and the like. Of these, basic catalysts are preferred. Although the usage-amount of a catalyst is not specifically limited, Preferably it is 0.0001 to 10 weight% with respect to the polymer to produce | generate, More preferably, it is 0.001 to 1 weight%.

As the polyol (PL2), other than (PL1), known polyols used for the production of polymer polyols (for example, JP 2005-162791 A, JP 2004-018543 A, JP 2006-016611 A, etc.) 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 the polyurethane resin.

  The AO includes those described above. Among these AOs, C2-8 are preferable from the viewpoint of the mechanical properties of the polyurethane resin, more preferably EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran, styrene oxide, and these. Two or more types of combined use (block addition and / or random addition), particularly preferably PO or a combination of PO and EO [EO content is 20% or less, preferably 15% or less, based on the weight of (PL), Preferably, it is 5 to 10%].

Specific examples of the AO adduct include a PO adduct of a known active hydrogen-containing compound (Japanese Patent Application Laid-Open No. 2005-162791, etc.) and PO and other 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 preferable range of the OH equivalent and Mn of (PL2) is the same as (PL) described later.

  OH equivalent of (PL) (OH value = 56,100 / determined by hydroxyl value using hydroxyl value (mgKOH / g) determined according to JIS K1557-1: 2007) is the viscosity of polymer polyol and polyurethane From the viewpoint of the mechanical properties of the resin, it is preferably 500 to 1,800, more preferably 800 to 1,600. Particularly preferably, it is 1,000 to 1,500.

  Mn of (PL) is preferably 500 to 10,200, more preferably 1,000 to 8,500, and particularly preferably 1,500 to 6,6 from the viewpoints of mechanical properties of the polyurethane resin, viscosity of the polymer polyol, and handling properties. 800.

  The content (% by weight) of the oxyethylene unit in (PL) is 0.1 to 20, preferably 0.1 to 15, more preferably 1.2 to 14, based on the weight of (PL). More preferably, it is 2-13, Most preferably, it is 5-10. If the proportion of (PL1) is less than 0.1% by weight, the reactivity of (PL) and the mechanical properties (wet heat compression strain) of the resulting polyurethane resin will be poor, and if it exceeds 20% by weight, the moldability of the polyurethane resin will be poor. Become.

The average added mole number x of EO per active hydrogen of polyol (PL) is preferably 20 or less, more preferably 15 or less, further preferably 12 or less, and most preferably from the viewpoint of the physical properties and mechanical strength of the urethane resin. 10 or less.
The primary OH conversion rate y (%) based on the molecular terminal hydroxyl group of the polyol (PL) is 70 to 100 mol%, and x and y (%) are the following formulas (1) and x are 10 to 10 when x is less than 10. When it is 20, the relationship of the following formula (2) is satisfied.
y ≧ 42x ^0.47 (1-x / 41) (1)
y ≧ 0.328x + 90.44 (2)
Further, when x is 7 or less, x and y (%) preferably satisfy the relationship of the following formula (1) ′, and more preferably satisfy the relationship of the following formula (1) ″.
y ≧ 45x ^0.47 (1-x / 41) (1) ′
y ≧ 47x ^0.47 (1-x / 41) (1) ''
When the relationship between x and y and x and y is within the above ranges, both hydrophobicity and reactivity are good.
As a method for adjusting the relationship between x and y so as to satisfy the above formulas (1) and (2), AO is added to the active hydrogen-containing compound in the presence of the specific catalyst (α) described above as the polyol (PL). It is preferable to use a polyol obtained by adding EO and further adding EO.

Here, the primary OH conversion ratio is obtained by ¹ H-NMR analysis method after esterifying (PL) in advance. Details of the ¹ H-NMR method will be specifically described below.
<Sample preparation method>
About 30 mg of a measurement 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 allowed to stand at 25 ° C. for about 5 minutes.
Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

<NMR measurement>
¹ H-NMR measurement is performed under normal conditions.
<Calculation method of primary OH ratio based on hydroxyl group at molecular end>
The signal derived from the methylene group to which the primary hydroxyl group is bonded is observed at around 4.3 ppm, and the signal derived from the methine group to which the secondary hydroxyl group is bonded is observed at around 5.2 ppm. Is calculated by the following formula.
Primary OH conversion rate (%) = [r / (r + 2q)] × 100
However,
r: integrated value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm. q: integrated value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm.

Regarding the total unsaturation t and OH equivalent s of the polyol (PL), from the viewpoint of mechanical strength and mechanical properties of the polyurethane resin, s is 500 to 1,800, and the relationship of the following formula (3) is satisfied. It is preferable to satisfy.
t ≦ 3 × 10 ⁻⁵ s−0.0006 (3)

Here, the total degree of unsaturation t is derived from an unsaturated group-containing product produced by a side reaction that occurs when the polyol (PL) is produced.
The total degree of unsaturation t is determined by ¹ H-NMR measurement of a polyether acetylated with trifluoroacetic anhydride (TFA) and a polyether without acetylation, respectively, and determined by the method described in JIS K1557-3: 2007. The unit is meq / g.

  The unsaturated group-containing product produced during the production of (PL) is produced with the PO addition reaction. Therefore, the large degree of total unsaturation in (PL) means that (PL) has a number of hydroxyl groups per molecule due to a side reaction during the production, and therefore the number of hydroxyl groups per molecule has a distribution. means. That is, it means that the number of moles of AO added per molecule has a distribution and the molecular weight distribution of PL is widened. The lower the total degree of unsaturation, the better the mechanical strength of the polyurethane resin.

  Therefore, the meaning of the above formula (3) means that the degree of unsaturation is not more than a specific value with respect to the OH equivalent, that is, the molecular weight distribution of (PL) with respect to the OH equivalent of (PL). Means not wide.

  In order for the polyol (PL) to satisfy the above formula (3), it is preferable to increase the amount of (PL1) used.

  In order for the polyol (PL) to satisfy the above formula (3), it is preferable to produce (PL) by adding 1,2-AO to an active hydrogen-containing compound in the presence of a specific catalyst (α).

  The content (% by weight) of the polymer particles (JR) in the polymer polyol (A) is, based on the weight of (A), 20 to 60 from the viewpoint of mechanical properties of the polyurethane resin and prevention of aggregation of (JR). More preferably, it is 25-58, Most preferably, it is 30-55. In addition, content of (JR) in (A) is measured by the method mentioned later.

<Content of polymer particles (JR)>
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 is the polymer particle content (% by weight).

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

  The content (% by weight) of the polyol (PL) in (A) is preferably 40 to 80, more preferably 42 to 75, and most preferably from the viewpoint of preventing aggregation of (JR) and mechanical properties of the polyurethane resin. 45-70.

  The viscosity (mPa · s) of (A) is preferably 1,250 to 12,000, more preferably 1,500 to 10,000, and most preferably 2,500 to 8,000 from the viewpoint of moldability. is there.

In the polymer polyol (A) of the present invention, from the viewpoint of moldability of the polyurethane resin, the content v (% by weight) of the polymer particles (JR) in the polymer polyol and the viscosity w (mPa · s) of the polymer polyol are as follows. It is preferable to satisfy | fill Formula (4) and (5), More preferably, it is satisfy | filling Formula (4) and (6).
w ≧ 250v−5000 (4)
w ≦ 450v-8400 (5)
w ≦ 450v-8600 (6)
The viscosity of the polymer polyol is measured by a method described in JIS K1557-5: 2007 at 25 ° C. using a Brookfield viscometer.

  In order to satisfy the above relationship between the viscosity and the content, the OH equivalent of PL used is preferably 500 to 1,800, more preferably 800 to 1,600. Particularly preferably, it is 1,000 to 1,500.

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 (D) (for example, US Pat. No. 3,383,351) Can be used.

As the dispersant (D), 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 (D) is reactive dispersion which has an ethylenically unsaturated group which can be copolymerized with an ethylenically unsaturated compound (E). And a non-reactive dispersant that does not copolymerize with (E).
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 (D),
[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). Reactive dispersants such as those described in Japanese Patent Publication No.

  As (D), it is preferable to use a vinyl oligomer dispersant (D1) and / or a reactive dispersant (D2) described below.

(D1) is a vinyl oligomer obtained by polymerizing an ethylenically unsaturated compound. As the ethylenically unsaturated compound constituting (D1), the same ethylenically unsaturated compound (E) as described above can be used.
Among these, from the viewpoint of the particle diameter of (JR), at least a part of the ethylenically unsaturated compound constituting (D1) is the same as the ethylenically unsaturated compound (E) constituting (JR). More preferably, 30% by weight or more of the ethylenically unsaturated compound constituting (D1) is the same as (E), then more preferably 70% by weight, particularly preferably 80% by weight. That's it.

  The weight average molecular weight (hereinafter abbreviated as Mw) of (D1) is 1,000 to 1,000,000 on the basis of polystyrene by gel permeation chromatography (GPC) measurement from the viewpoint of the particle diameter of (JR). Preferably, it is 600,000-750,000. In addition, (D1) is soluble in polyol (PL) from the viewpoint of the particle diameter of (JR) [5% by weight (D1) is uniformly mixed in (PL) based on the total weight of (D1) and (PL). It is desirable that the transmittance of the laser beam of the obtained mixture is 10% or more.

  The production of (D1) can be carried out by an ordinary polymerization method of an ethylenically unsaturated compound except that the degree of polymerization is adjusted so that the weight average molecular weight is 1,000 to 1,000,000. For example, it is a method of polymerizing the ethylenically unsaturated compound (E) in the presence of a polymerization initiator described later, if necessary, in a solvent. Further, (D1) may be obtained by polymerizing (E) in polyol (PL). In this case, the polymerization concentration is preferably 1 to 40%, more preferably 5 to 20%. You may use for the production of a polymer polyol as it is, without refine | purifying what was obtained by superposition | polymerization. The polymerization initiator is used in a relatively large amount, for example, preferably 2 to 30%, more preferably 5 to 20% based on the mass of the total ethylenically unsaturated compound.

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

  If necessary, chain transfer agents such as alkyl mercaptans (dodecyl mercaptan, mercaptoethanol, etc.), alcohols (isopropyl alcohol, methanol, 2-butanol, etc.), halogenated hydrocarbons (carbon tetrachloride, carbon tetrabromide, chloroform, etc.) ), Polymerization can be carried out in the presence of 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 higher than the decomposition temperature of the polymerization initiator (usually 50 to 250 ° C., preferably 80 to 200 ° C., particularly preferably 100 to 180 ° C.), and can be performed under atmospheric pressure or under pressure. it can.

  When (D1) is used, the amount (% by weight) of (D1) is preferably 0.01 to 100 based on the weight of (E) from the viewpoint of the particle diameter of (JR) and the mechanical strength of urethane. More preferably, it is 0.1-80, Most preferably, it is 1-60.

  The reactive dispersant (D2) contains a monofunctional active hydrogen compound (c) having at least one polymerizable unsaturated group bonded to a saturated polyol (b) via a polyisocyanate (f). It is a dispersant comprising a nitrogen bond-containing unsaturated polyol.

As (b) constituting the reactive dispersant (D2), the same ones exemplified as the aforementioned (PL) can be used. (B) and (PL) may be the same or different.
The number of hydroxyl groups in one molecule of (b) is at least 2, preferably 2-8, and more preferably 3-4.

(C) used to obtain (D2) is a compound having one active hydrogen-containing group and at least one polymerizable unsaturated group. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, an imino group, a carboxyl group, and an SH group, and a hydroxyl group is particularly preferable.
The polymerizable unsaturated group (c) is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably 1 to 3, particularly preferably 1. That is, an unsaturated monohydroxy compound having one polymerizable double bond is preferable as (c).
Examples of the unsaturated monohydroxy compound include monohydroxy substituted unsaturated hydrocarbon, monoester of unsaturated monocarboxylic acid and dihydric alcohol, monoester of unsaturated dihydric alcohol and monocarboxylic acid, alkenyl side chain Examples thereof include phenol having a group and unsaturated polyether monool.

Monohydroxy substituted unsaturated hydrocarbons include C3-6 alkenols such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol; alkynol such as Propagyl alcohol is mentioned.
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 2 to 12 carbon dihydric alcohols such as propylene glycol and butylene glycol), and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2 -Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like.

Examples of monoesters of unsaturated dihydric 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 hydroxystyrene and hydroxy α-methylstyrene.
As the unsaturated polyether monool, an alkylene oxide (C2-8) 1 to 50 mol adduct of the above monohydroxy-substituted unsaturated hydrocarbon or phenol having the alkenyl side group [for example, polyoxyethylene (C2-10) Monoallyl ether] and the like.

Examples of (c) other than the unsaturated monohydroxy compound include the following.
Examples of (c) 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]; (c) having a carboxyl group is the unsaturated monocarboxylic acid; and (c) having an SH group is And compounds corresponding to saturated monohydroxy compounds (OH is replaced by SH).
Examples of (c) having two or more polymerizable double bonds include poly (meth) allyl ethers of trihydric, tetrahydric, polyhydric or higher polyhydric alcohols or polyesters with unsaturated carboxylic acids. [For example, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, etc.].

Among these, preferred compounds are C3-6 alkenols, monoesters of C3-8 unsaturated monocarboxylic acids and C2-12 dihydric alcohols, and phenols having alkenyl side groups, more preferably (meta ) Monoesters of acrylic acid with ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, particularly preferably 2-hydroxyethyl (meth) acrylate.
The molecular weight of (c) is not particularly limited, but is preferably 1,000 or less, particularly 500 or less.

  The polyisocyanate (f) is a compound having at least two isocyanate groups, and is an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, a modified product of these polyisocyanates (urethane) Groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups or oxazolidone group-containing modified products), and mixtures of two or more of these.

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

Examples of the alicyclic polyisocyanate include C4-16 alicyclic diisocyanate. Specific examples include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic isocyanate include C8-15 araliphatic diisocyanate. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
Of these, aromatic diisocyanates are preferred, and 2,4- and 2,6-TDI are more preferred.

The nitrogen-containing bond of the reactive dispersant (D2) is generated by a reaction between an isocyanate group and an active hydrogen-containing group. When the active hydrogen-containing group is a hydroxyl group, a urethane bond is mainly generated, and an amino group In some cases, predominantly urea bonds are formed. 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 (b) and the isocyanate group of the polyisocyanate (f), the active hydrogen-containing group of the unsaturated monofunctional active hydrogen compound (c) and the (f) Some are produced by reaction with isocyanate groups.

From the viewpoint of dispersion stability of the polymer polyol, the average value of the number of hydroxyl groups in one molecule of (D2) is usually 2 or more, preferably 2.5 to 10, and more preferably 3 to 7. The average value of the number of unsaturated groups in one molecule of (D2) is preferably from 0.8 to 2, more preferably from 0.9 to 1.2.
The viscosity of (D2) is preferably from 2,000 to 20,000 mPa · s / 25 ° C., more preferably from 3,000 to 9,000 mPa from the viewpoint of the particle diameter of (JR) and the moldability of the polyurethane resin. -S / 25 degreeC.

The method for producing the reactive dispersant (D2) is not particularly limited.
As a preferable method, a method in which polyisocyanate (f) is added to a mixture of unsaturated monofunctional active hydrogen compound (c) and saturated polyol (b) and the reaction is carried out in the presence of a catalyst, if necessary, (c) And (f), if necessary, in the presence of a catalyst to produce an unsaturated compound having an isocyanate group, and reacting this with (b). The latter method is the most preferable method because a nitrogen-containing bond-containing unsaturated polyol with less generation of by-products such as a compound having no hydroxyl group is obtained.
Alternatively, instead of (c) or (b), the precursor may be used to react with (f), and then the precursor portion may be modified to form (D2). [For example, after reacting with an isocyanate, an unsaturated monocarboxylic acid or an ester-forming derivative thereof is reacted to introduce an unsaturated group, and after reacting with an isocyanate, jumping with an alkylene dihalide, dicarboxylic acid or the like (D2) Form〕

Examples of the catalyst at the time of the reaction include a commonly used urethanization catalyst, a tin catalyst (dibutyltin dilaurate, stannous octoate, etc.), other metal catalysts (tetrabutyl titanate, etc.), amine catalysts ( Triethylenediamine or the like). Of these, tetrabutyl titanate is preferred.
The amount of the catalyst is preferably 0.0001 to 5%, more preferably 0.001 to 3%, based on the mass of the reaction mixture.

The reaction ratio of these three components is based on the total amount used in the reaction, and the equivalent ratio of the active hydrogen-containing group (c) and (b) to the isocyanate group (f) is (1.2 to 4): 1. Is more preferable, and (1.5-3): 1 is more preferable.
Further, the amount of (c) used for the reaction with respect to 100 parts of (b) is preferably less than 2 parts, more preferably 0.5 to 1.8 parts. Above and below, parts refer to parts by weight.
In addition, a large excess of (b) that reacts with (f) is used to form a mixture of (D2) and (b), and unreacted (b) is left as it is without separation of polyol (A). The method used as a part of can also be taken.

The reactive dispersant (D2) obtained by the above method may be a single compound, but in many cases, it is a mixture of various compounds such as a compound represented by the following general formula (2).

；Ｔ’はＨ又は炭素数１〜１２のアルキル基；ｃは１又はそれ以上の整数；ｊは１以上の整数である。ただしｑ₁−ｇ≧０、ｈ−ｊ−１≧０である。なお、ＯＨ基の合計は２以上である。］ [In the formula, Z is an h-valent residue of (f) (where h is an integer of 2 or more); T is a residue of (c) (provided that it has a polymerizable unsaturated group); A ₁ is q residues of _monovalent polyol [(b), or (b) and (f) OH prepolymer from], a ₂ is from q ₂ dihydric polyol [(b), or (b) and (f) OH prepolymer] residue (where q ₁ and q ₂ are integers of 2 or more); X is a single bond, O, S, or

T ′ is H or an alkyl group having 1 to 12 carbon atoms; c is an integer of 1 or more; j is an integer of 1 or more; However, q ₁ −g ≧ 0 and h−j−1 ≧ 0. The total number of OH groups is 2 or more. ]

That is, one (b) and one (c) are combined through one (f), and a plurality of (c) is one (b) through one (f). ) And a combination of 3 or more (b) and (c) via a plurality of (f). Further, as by-products other than these, (b) comrades bonded via (f) (nitrogen-containing bond-containing polyol having no unsaturated group), (c) comrades bonded via (f) (A nitrogen-containing bond-containing unsaturated compound having no hydroxyl group) may be formed, and unreacted (b) or (c) may be included.
Although this mixture can be used as a dispersant as it is, those containing a nitrogen-containing bond-containing polyol having no unsaturated group or a nitrogen-containing bond-containing unsaturated compound having no hydroxyl group are preferred, and these impurities which can be further removed. It can also be applied after removing.
Moreover, since the unsaturated group in (D2) is located at or near the terminal of the molecular chain of the polyol, it is easy to copolymerize with the monomer.

(D2) is calculated by the following formula (7), and the average value of the ratio of the number of unsaturated groups to the nitrogen-containing bond derived from the NCO group of (f) in one molecule: K is 0.1 to 0.4 (B), (c) and (f) are reacted at such a ratio.
H = [number of moles of (c) × number of unsaturated groups of (c)] / [number of moles of (f) × number of NCO groups of (f)] (7)
The value of H is more preferably 0.1 to 0.3, and particularly preferably 0.2 to 0.3. When the value of H is within the above range, the dispersion stability of the polymer polyol is particularly good.

  The amount (% by weight) of (D2) used in the case of using (D2) is preferably 2 to 20, more preferably 4 to 4, based on the weight of (E), from the viewpoint of dispersibility and the viscosity of the polymer polyol. 15, particularly preferably 6-10.

  As the radical polymerization initiator (K), compounds that generate free radicals to initiate polymerization, such as azo compounds and peroxides (for example, those described in JP-A-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 based on the weight of (E) from the viewpoint of the polymerization rate of (E) and the mechanical properties of the polyurethane resin. -5, particularly preferably 0.2-2.

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. Among these, an aromatic hydrocarbon solvent is preferable 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 resin, 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 after the completion of the polymerization reaction from the viewpoint of the mechanical properties of the polyurethane resin.

In radical polymerization, a chain transfer agent (G) may be used if necessary. 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 2, based on the weight of (E), from the viewpoint of the viscosity of (A) and the mechanical properties of the polyurethane resin. 1.

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 can be carried out either batchwise or continuously.

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

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 shearing force 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 resin, and From the viewpoint of mechanical properties of the polyurethane resin, 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 producing a polyurethane resin (polyurethane elastomer, polyurethane foam, etc.). That is, (A) or a polyol component (Po) containing (A) and an isocyanate component (Is) comprising a polyisocyanate [hereinafter, a composition comprising (Po) and (Is) is referred to as a polyurethane resin-forming composition. There is. ] Can be reacted by a known method (for example, the method described in JP-A-2004-263192) or the like to obtain a polyurethane resin.

As the polyol component (Po), in addition to (A) of the present invention, a polyol and a known polymer polyol other than (A) may be used as a raw material when producing a polyurethane resin as long as the effects of the present invention are not impaired. May be used.
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 resin based on the weight of (A), Preferably it is 1-1000.
Based on the weight of (A), the use amount (% by weight) of a known polymer polyol other than (A) is based on the mechanical properties of the polyurethane resin and the reduction of clogging of the strainer and discharge port of the polyurethane resin production apparatus. Preferably it is 1-100.

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

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 resins can be used.
Among these, 2,4- and 2,6-TDI, a mixture of these isomers, crude TDI (residue when TDI is purified); 4,4 are preferable from the viewpoint of mechanical properties of the polyurethane resin. '-And 2,4'-MDI, mixtures of these isomers, crude MDI (residue when MDI is purified); and urethane groups, carbodiimide groups, allophanate groups, ureas derived from these polyisocyanates It is a modified polyisocyanate containing a 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 the polyurethane resin can be adjusted as appropriate from the viewpoint of the mechanical properties of the polyurethane resin. Is more preferable, 85-120 is more preferable, and 95-115 is particularly preferable.

  In order to accelerate the reaction during the production of the polyurethane resin, various catalysts used in the urethanization reaction (for example, those described in JP-A-2005-162791) can be contained in the polyurethane resin-forming composition. The usage-amount (weight%) of a catalyst is 10 or less normally based on the total weight of a polyurethane resin-forming composition, Preferably it is 0.001-5.

In the production of polyurethane resin, various foaming agents (for example, those described in JP-A-2006-152188) [water, HFC (hydrofluorocarbon), HCFC (hydrochlorofluorocarbon), methylene chloride, etc.] are formed into polyurethane resin. It can be made into a polyurethane foam by making it contain in an adhesive composition. 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 resin-forming composition.
When producing a polyurethane foam, a foam stabilizer can be further contained in the polyurethane resin-forming composition if necessary. 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 resin-forming composition.

In the production of the polyurethane resin, a flame retardant can be further contained in the polyurethane resin-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 resin-forming composition.

  In the production of polyurethane resins, as long as the effects of the present invention are not impaired, reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides, and fillers (carbon The polyurethane resin-forming composition may contain at least one other additive selected from the group consisting of (including black).

The polyurethane resin 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 the polyurethane resin, a conventionally used production apparatus (such as a low-pressure or high-pressure machine) can be used. In the case of no solvent, an apparatus such as a kneader or an extruder can be used. Moreover, when manufacturing non-foaming or foaming polyurethane resin, a closed mold or an open mold can be used.

  The polyurethane resin produced by using the polymer polyol (A) of the present invention is excellent in mechanical properties and can be applied to conventional polyurethane resin applications (urethane foam, urethane elastomer, urethane coating agent, etc.). In particular, it can be suitably used as a cushion material for automobiles from the viewpoints of moldability and mechanical properties when producing polyurethane resin.

  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 ratio refer to parts by weight, weight%, and weight ratio, respectively, unless otherwise specified.

The composition and symbols of the raw materials used in the following examples are as follows.
(1) Polyol polyol (PL-1): 8 mol of PO was added to 1 mol of pentaerythritol in the same manner as in Example 1 of JP 2000-344881 A using tris (pentafluorophenyl) borane as a catalyst. Thereafter, after removing the catalyst component, 10.4 mol of EO was further added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (reaction product weight basis), reaction temperature: 95 to 105 ° C.], and water was added by a conventional method. Polyol polyol (PL-2) having a hydroxyl value of 37.4, an EO unit content of 8%, and a primary hydroxyl group ratio of 82 mol%, from which potassium oxide has been removed. JP-A 2000-344881 In the same manner as in Example 1, 49.7 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst, and then the catalyst component was removed. Further, 12 mol of EO was added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (based on reaction product weight), reaction temperature: 95 to 105 ° C.], and potassium hydroxide was removed by a conventional method. Polyol polyol (PL-3) having a ratio of 48.1, EO unit content = 15%, primary hydroxyl group 86 mol%: 1 mol of glycerin was added to Tris (in the same manner as in Example 1 of JP-A-2000-344881). 64.2 mol of PO was added using pentafluorophenyl) borane as a catalyst, and then the catalyst components were removed. Then, 15.3 mol of EO was added using potassium hydroxide as a catalyst [catalyst consumption 0.3% (reaction product (Weight basis), reaction temperature 95 to 105 ° C.], potassium hydroxide was removed by a conventional method, hydroxyl value = 37.4, EO unit content = 14%, ratio of primary hydroxyl group 8 Mol% polyol polyol (PL-4): 8 mol of PO was added to 1 mol of pentaerythritol in the same manner as in Example 1 of JP-A-2000-344881 using tris (pentafluorophenyl) borane as a catalyst. Thereafter, after removing the catalyst component, 24.0 mol of EO was further added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (reaction product weight basis), reaction temperature: 95 to 105 ° C.]. Polyol polyol (PL-5) having a hydroxyl value of 37.4, an EO unit content of 17.5%, and a primary hydroxyl group ratio of 90 mol%, from which potassium oxide has been removed: JP-A 2000-344881 In the same manner as in Example 1, 53.2 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst, and then the catalyst component was added. After removal, 30.0 mol of EO was further added using potassium hydroxide as a catalyst [catalyst consumption 0.3% (reaction product weight basis), reaction temperature 95 to 105 ° C.], and potassium hydroxide was removed by a conventional method. Polyol having a hydroxyl value of 37.4, an EO unit content of 14%, and a primary hydroxyl group ratio of 95 mol%

Polyol (PL-6): 7 mol of PO and 15.9 mol of EO were added in block order in this order to 1 mol of glycerin using potassium hydroxide as a catalyst [amount of catalyst used 0.3% (based on reaction product weight), reaction Temperature 95-105 ° C.], potassium hydroxide removed by a conventional method, hydroxyl value = 33.0, terminal EO unit content = 14%, polyol polyol (PL-7) with primary hydroxyl group ratio 78 mol%: penta Block addition of PO 106.4 mol and EO 16.0 mol in this order using potassium hydroxide as a catalyst to 1 mol of erythritol [amount of catalyst used 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.] Polyol polyol (PL-) having a hydroxyl value of 32.1, a terminal EO unit content of 10%, and a primary hydroxyl group ratio of 73 mol%, from which potassium hydroxide was removed by a conventional method ): 6 mol of PO and 14.0 mol of EO were added in block order in this order to 1 mol of glycerin using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% (based on weight of reaction product), reaction temperature: 95 to 105 ° C. ] Polyol polyol (PL-9) having a hydroxyl value of 37.4, a terminal EO unit content of 14%, and a primary hydroxyl group ratio of 76 mol%: potassium erythritol was removed by a conventional method: water in 1 mol of pentaerythritol 82.8 mol of PO and 24.0 mol of EO were added in block order in this order using potassium oxide as a catalyst [catalyst consumption 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.], and hydroxylated by a conventional method. Polyol polyol (PL-10) having a hydroxyl value of 37.4, a terminal EO unit content of 17.5%, and a primary hydroxyl group ratio of 80 mol%, from which potassium has been removed: pentae Block addition of 117.8 mol of PO and 24.5 mol of EO in this order using potassium hydroxide as a catalyst to 1 mol of sitol (amount of catalyst used 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.) Polyol polyol (PL-11) having a hydroxyl value of 28.1, a terminal EO unit content of 13.5%, and a primary hydroxyl group ratio of 81 mol%: 1 mol of pentaerythritol, with potassium hydroxide removed by a conventional method In the same manner as in Example 1 of Japanese Utility Model Publication No. 2000-344881, 124.4 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst, the catalyst component was removed, and EO14. 4 mol was added [catalyst consumption 0.3% (based on reaction product weight), reaction temperature 95 to 105 ° C.] Polyol polyol (PL-12) having a hydroxyl value of 37.4, an EO unit content of 8.0%, and a primary hydroxyl group ratio of 84 mol%: PO64.7 using 1 mol of glycerol and potassium hydroxide as a catalyst. Mole and 22.7 mol of EO were block-added in this order [catalyst consumption: 0.3% (reaction product weight basis), reaction temperature: 95 to 105 ° C.], and potassium hydroxide was removed by a conventional method. 33.7, polyol with terminal EO unit content = 20%, primary hydroxyl group ratio 84 mol%

(2) Radical polymerization initiator K-1: 1,1′-azobis (2-methylbutyronitrile) [trade name “V-59”, manufactured by Wako Pure Chemical Industries, Ltd.]

(3) Dispersant D-1: ACN: St = 70: 30 Aw ratio of ACN: St = 70: 30 Mw = 600,000 ACN-St copolymer oligomer type non-reactive dispersant {this oligomer type dispersant Was mixed with polyol (PL-6) so that the content was 10% by weight. Hydroxyl value of this mixture = 29.0}
D-2: Dispersant described in Production Example 1 of JP-A-2002-308920 {Hydroxyl value = 20, number of unsaturated groups obtained by jointing polyol (PL-12) and 2-hydroxyethyl methacrylate with TDI / Reactive dispersant with nitrogen-containing group bond number = 0.22 / 1}

(4) Polyisocyanate CE-729: TDI / polymeric MDI = 80/20 (weight ratio), trade name “CE-729” (manufactured by Nippon Polyurethane Industry Co., Ltd.)

(5) Catalyst Catalyst A: Trade name “TEDAL-33” (triethylenediamine / dipropylene glycol = 33/67% solution) [manufactured by Tosoh Corporation]
Catalyst B: Trade name “TOYOCAT ET” (bis-2-dimethylaminoethyl ether / dipropylene glycol = 33/67 (%) solution) [manufactured by Tosoh Corporation]

(6) Foam stabilizer SZ-1346 (polyethersiloxane polymer) [manufactured by Nippon Unicar Co., Ltd.]

The measurement and evaluation methods in the examples are as follows.
<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

<Examples 1 to 6 and Comparative Examples 1 to 5>
Two continuous polymerization equipment (2L SUS pressure-resistant reaction vessel connected with temperature controller, stirring blade, liquid feed line, and overflow line) are prepared. The first overflow line is connected to the inlet of the second polymerization tank. Connect and place in series. A raw material supply pump is installed in the liquid feed line to the first tank. In each of the first and second polymerization tanks, 2000 g parts of polyol (PL-1 in the case of Examples 2 to 6 and Comparative Examples 1 to 5, respectively) and the polyols shown in Table 1 or Table 2, respectively. The same polyol is charged.In the case of a plurality of polyols, 2000 g of the mixture of the number of parts shown in Table 1 or Table 2 is charged) and heated to 125 ° C. with stirring. Next, a raw material liquid in which the polyol (PL), the radical polymerization initiator (K), the ethylenically unsaturated compound (E), and the dispersant (D) having the composition shown in Table 1 or 2 are previously uniformly mixed by a raw material supply pump is prepared. The reaction solution which was continuously injected into the first polymerization tank by the raw material supply pump at 270 ml / min and overflowed from the first polymerization tank was continuously fed to the second polymerization tank. The reaction liquid overflowed from the second polymerization tank after 1 hour from the start of liquid feeding was stocked in a SUS receiving tank to obtain a polymer polyol intermediate. Next, the polymer polyol intermediate was charged into a glass Kolben equipped with a temperature controller and a stirring blade, and was stripped at 125 ° C. under a reduced pressure of 2666-3999 N / m ^{2 for} 3 hours to leave a remaining ethylenically unsaturated compound. Was distilled off to produce polymer polyols (F-1) to (F-6) and (R-1) to (R-5). The results are shown in Table 1 or Table 2.

<Examples 7 to 12 and Comparative Examples 6 to 10> [Production of polyurethane foam]
The polymer polyols (F-1) to (F-6) obtained in Examples 1 to 6 and the comparative polymer polyols (R-1) to (R-5) obtained in Comparative Examples 1 to 5 were used. In the order of the number of polymer polyols, polyol (PL-12), SZ-1346, water, catalyst A, and catalyst B in the order of parts of the foaming formulation shown in Table 3, put them in a 1 L capacity paper cup at room temperature (25 ± 2 ° C) The mixture (PPL) and polyisocyanate stirred in step 1 were each adjusted to 25 ± 2 ° C. After temperature control, polyisocyanate (CE-729) was added to the mixture (PPL), and the mixture was stirred and mixed with a stirrer (Homodisper: manufactured by Tokushu Kika Co., Ltd., stirring conditions: 2000 rpm × 7 seconds). Immediately after stirring and mixing, the contents were put into a mold (sealed mold, mold size 40 × 40 × 10 (H) cm) that had been temperature-controlled at 60 ± 5 ° C. in advance. After 6 minutes from the start of stirring, the polyurethane foam was removed from the mold to produce a polyurethane foam. The polyurethane foam was evaluated and the results are shown in Table 3.

<Method for evaluating physical properties of foam>
(1) Core density (kg / m ³ ): Conforms to JIS K6400-1997 [Item 5].
(2) Foam hardness (25% ILD) (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) Compressive residual strain (%): compliant with JIS K6382-1995 [Item 5.5].

  From the results of Tables 1 to 3, the polymer polyols of Examples 1 to 6 had lower viscosities than Comparative Example 1. Moreover, the polymer polyol of Examples 1-6 had a low total unsaturation compared with Comparative Examples 1-5. And it turns out that the polyurethane foam manufactured using the polymer polyol of Examples 1-6 has improved foam physical property compared with the case of the polymer polyol of Comparative Examples 1-5. In particular, the foam hardness (25% ILD) value is improved, and it can be seen that the tensile strength is equal to or higher.

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

Claims (8)

In a polymer polyol in which polymer particles (JR) containing an ethylenically unsaturated compound (E) as a structural unit are contained in a polyol (PL), the primary OH conversion rate based on the molecular terminal hydroxyl group of (PL) is 70. ˜100 mol%, the content of oxyethylene units of (PL) is 0.1 to 20% by weight based on the weight of (PL), and (PL) is the average of ethylene oxide per active hydrogen 1,2-alkylene oxide having 2 or more carbon atoms satisfying the relationship of the following formula (1) when the added mole number x is the primary OH conversion rate y and x is less than 10 and 10 to 20: A polymer polyol (A) which is a polyether polyol obtained by randomly and / or block-adding an alkylene oxide mainly composed of
y ≧ 42x ^0.47 (1-x / 41) (1)
y ≧ 0.328x + 90.44 (2) The polymer polyol according to claim 1, wherein the polyol (PL) has an OH equivalent of 500 to 1,800. The polymer polyol according to claim 1 or 2, wherein s is 500 to 1,800 and satisfies the relationship of the following formula (3) with respect to the total unsaturation t and OH equivalent s of the polyol (PL).
t ≦ 3 × 10 ⁻⁵ × s−0.0006 (3) The median diameter of polymer particles (JR) based on the volume standard of the particle size distribution when the range of 0.040 to 262 μm measured by a laser diffraction / scattering particle size distribution measuring device is divided into 65 is 0.1 to 0.55 μm. The polymer polyol according to any one of claims 1 to 3. The polymer particles (JR) are polymer particles formed by polymerizing an ethylenically unsaturated compound (E) in the presence of the following dispersant (D1) and / or dispersant (D2). Polymer polyol in any one of 1-4.
Dispersant (D1): Vinyl oligomer dispersant having a weight average molecular weight of 1,000 to 1,000,000 (D2): Monofunctional activity having a saturated polyol (b) and at least one polymerizable unsaturated group The hydrogen compound (c) is bonded through the polyisocyanate (f), and the average value of the ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule is 0.1 to 0. 4 Nitrogen-containing bond-containing unsaturated polyol Content 1 (% by weight) of polymer particles (JR) based on the weight of the polymer polyol and the viscosity w (mPa · s) of the polymer polyol satisfy the following formulas (4) and (5): The polymer polyol according to any one of the above.
w ≧ 250v−5000 (4)
w ≦ 450v-8400 (5) In a method for producing a polyurethane resin by reacting a polyol component and an isocyanate component, the polyol component contains 10 to 100% by weight of the polymer polyol according to any one of claims 1 to 6 based on the weight of the polyol component. Manufacturing method of resin. The cushion material for vehicle seats which comprises the polyurethane resin obtained by the manufacturing method of Claim 7.