JP2010116429A - Polymer polyol composition for urethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer polyol composition from which a polyurethane resin having excellent hydrolysis resistance and oxidation stability can be produced, and to provide a urethane resin-forming composition, for solving such a problem that a polyurethane resin such as urethane foam and polyurethane elastomer using a polymer polyol obtained by polymerization of vinyl monomers in a polyether polyol has poor hydrolysis resistance and oxidation stability. <P>SOLUTION: The polymer polyol composition for a urethane resin contains a dispersion medium containing a castor oil fatty acid ester-based polyol and polymer fine particles dispersed in the dispersion medium. A urethane resin-forming composition and a urethane resin are prepared by using the above composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer polyol composition for urethane resin, a polyurethane resin-forming composition using the same, and a polyurethane resin.

  Polymer compositions and mixtures obtained by polymerizing vinyl monomers in polyether polyols are generally referred to as polymer polyols and are widely used as raw materials for polyurethane resins such as polyurethane foams and polyurethane elastomers (for example, patents). Reference 1 and 2).

Japanese Patent Laid-Open No. 3-97715 JP 2008-13761 A

  However, polyurethane resins such as urethane foams and polyurethane elastomers using a polymer polyol obtained by polymerizing a vinyl monomer in a polyether polyol have a problem of poor hydrolysis resistance and oxidation stability. An object of the present invention is to provide a polymer polyol composition and a urethane resin-forming composition capable of producing a polyurethane resin excellent in hydrolysis resistance and oxidation stability.

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, the present invention provides a polymer polyol composition for urethane resin (hereinafter simply referred to as a polymer) comprising a dispersion medium containing a castor oil fatty acid ester-based polyol and polymer fine particles dispersed in the dispersion medium. A polyol composition), and a urethane resin-forming composition and a urethane resin using the same.

  The polyurethane resin obtained by using the polymer polyol composition of the present invention is excellent in hydrolysis resistance, oxidation stability and heat resistance.

  In the present invention, castor oil fatty acid ester-based polyols include castor oil, hydrogenated castor oil, partially dehydrated castor oil, low molecular polyol having a molecular weight of 60 to 300, polyether polyol having a number average molecular weight of 100 to 2000, castor oil or water. Examples thereof include compounds obtained by transesterification with added castor oil or esterification with castor oil fatty acid or hydrogenated castor oil fatty acid.

  Hydrogenated castor oil is a hydrogenated part or all of the double bond of castor oil. Partially dehydrated castor oil is one in which a portion of the hydroxyl group has been eliminated by the dehydration reaction of castor oil. Usually, the hydroxyl value of partially dehydrated castor oil is 100 to 160 mgKOH / g, preferably 110 to 130 mgKOH / g. Castor oil fatty acid and hydrogenated castor oil fatty acid are fatty acids obtained by hydrolysis of castor oil and hydrogenated castor oil, respectively.

  Examples of the low molecular polyol include polyols having 2 to 24 carbon atoms (hereinafter abbreviated as C) such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, triglyceride, and the like. And methylolpropane, pentaerythritol, hydrogenated bisphenol A, hexanetriol, sorbitol, shoelacese, and mixtures of two or more thereof. The molecular weight of the low molecular weight polyol is preferably 60 to 300.

  As the polyether polyol, an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide is added to the low molecular weight polyol or a polyhydric phenol such as bisphenol A or hydroquinone, or an amine compound such as ammonia, ethylamine, ethylenediamine, or ethanol. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (PTMG), propylene oxide adduct of glycerin, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, etc. Can be mentioned. The number average molecular weight of the polyether polyol is preferably from 100 to 2,000.

  The polymer of the polymer fine particles is a polymer insoluble in castor oil fatty acid ester-based polyol, for example, one or more kinds of vinyl monomers such as polyethylene, polystyrene, polyalkyl methacrylate, polyacrylonitrile, polystyrene / acrylonitrile copolymer, etc. Examples thereof include a polymer obtained by a polymerization reaction, a polymer obtained by a polycondensation reaction such as polyethylene terephthalate, 6,6-nylon, and a phenol resin, and a polymer obtained by a polyaddition reaction such as a polyurethane resin. Among these polymers, a polymer obtained by polymerization of at least one vinyl monomer is preferable because it can be synthesized in a castor oil fatty acid ester-based polyol.

  Examples of vinyl monomers include aliphatic hydrocarbon monomers such as ethylene and propylene; aromatic vinyl monomers such as styrene, α-methylstyrene, and hydroxystyrene, (meth) acrylonitrile, (meth) acrylamide, diaminoethyl (meta ) Acrylates, morpholinoethyl (meth) acrylates, nitrogen-containing vinyl monomers such as vinylpyrrolidone; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc. It is done.

Examples of a method for dispersing polymer fine particles in a dispersion medium containing a castor oil fatty acid ester-based polyol include the following.
(1) A method of directly obtaining a polymer fine particle dispersion by polymerizing a vinyl monomer in a dispersion medium containing a castor oil fatty acid ester-based polyol.
(2) A method in which a polymer solution dissolved in another organic solvent is added to a dispersion medium containing a castor oil fatty acid ester-based polyol, and if necessary, the solvent is removed to precipitate and disperse polymer fine particles.
(3) A method of adding a solution in which polymer fine particles are dispersed in another organic solvent to a dispersion medium containing castor oil fatty acid ester polyol, and removing the solvent as necessary.
(4) A method of adding polymer fine particles obtained by pulverizing polymer fine particles or bulk polymer obtained by isolation after emulsion polymerization or dispersion polymerization to a dispersion medium containing castor oil fatty acid ester polyol. Among these methods, the method (1) is preferable because it requires fewer steps.

  An example of the case where a polymer fine particle dispersion is directly obtained by radical polymerization of a vinyl monomer in a dispersion medium containing a castor oil fatty acid ester-based polyol is shown below. A reaction vessel is charged with castor oil fatty acid ester polyol and, if necessary, an organic medium described later. In a separate container, a vinyl monomer and, if necessary, a castor oil fatty acid ester-based polyol and a dispersant described later are charged and stirred to obtain a vinyl monomer solution. In a separate container, a polymerization initiator and, if necessary, a castor oil fatty acid ester polyol or an organic medium are charged and mixed by stirring to obtain a polymerization initiator solution. The reaction vessel is stirred and heated, and when the polymerization temperature is reached, a vinyl monomer solution and a polymerization initiator solution are added dropwise to conduct a polymerization reaction. After completion of the polymerization reaction, if necessary, the pressure is reduced and the remaining monomer and the organic medium are distilled to obtain a polymer polyol composition. In addition, although superposition | polymerization temperature changes with initiators to be used, it is 70-180 degreeC normally, Preferably it is 100-160 degreeC. In addition to the one-stage batch polymerization reaction, a multistage batch reaction or a continuous reaction can be used.

  Examples of the polymerization initiator include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (N-butyl-2- Azo compounds such as methylpropionamide) or peroxides such as benzoyl peroxide, lauroyl peroxide, and dibutyl peroxide. The amount of the polymerization initiator used is preferably from 0.0001 to 20%, more preferably from 0.001 to 15%, particularly preferably from 0.005 to 10%, based on the total weight of the vinyl monomers. Hereinafter, “%” represents “% by weight” unless otherwise specified.

  In the present invention, a dispersant can be used for dispersing the polymer fine particles. Use of the dispersant facilitates control of the volume average particle diameter of the polymer fine particles, and increases the dispersion stability of the polymer fine particles in the polymer polyol composition. The composition and structure of a suitable dispersing agent varies depending on the polymer, but in general, a part having an affinity for the polymer and a compound (a) having an affinity for the dispersion medium, or a part having an affinity for the dispersion medium and the polymer are incorporated in the polymer. Compound (b) having a possible reactive group. For example, in the case of a polymer containing styrene, propylene oxide adducts of styrenated phenol, propylene oxide adducts of bisphenol A are examples of (a), and the styrenated phenol or bisphenol A portion has an affinity for styrene. The polypropylene oxide portion has an affinity with a castor oil fatty acid ester polyol. In the case of a polymer obtained by polymerization of a vinyl monomer, examples of (b) include castor oil or partially dehydrated castor oil, hydroxyethyl (meth) acrylate, and TDI (2,4- and / or 2,6-tolylene. Isocyanates) or reaction products of polyisocyanates such as MDI (2,4′- and / or 4,4′-diphenylmethane diisocyanate).

  In the present invention, the main component of the dispersion medium is castor oil fatty acid ester-based polyol, and the weight percentage of castor oil fatty acid ester-based polyol in the dispersion medium is usually 60% or more, preferably 80% or more. If necessary, an organic medium such as the low molecular polyol, the polyol compound such as the polyether polyol, the polyester polyol and the polycarbonate diol, the hydrocarbon compound such as isoparaffin, toluene and xylene, the esters such as diisononyl phthalate and octyl sebacate, etc. Can be contained. Among these organic media, polyether polyols are preferable from the viewpoint of compatibility with castor oil fatty acid ester polyols and viscosity. The total weight of these organic media is usually 40% or less, preferably 20% or less in the dispersion medium.

  In the present invention, the amount of polymer fine particles in the polymer polyol composition is usually 10 to 80%, preferably 20 to 70%, particularly preferably 25 to 60% from the viewpoints of heat resistance and viscosity.

  In the present invention, the volume average particle diameter of the polymer fine particles is 0.01 to 60 μm, preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm from the viewpoints of viscosity and stability. The volume average particle diameter can be measured by a dynamic light scattering method described later.

  The polyurethane resin of the present invention includes a polyurethane resin obtained by reacting the polymer polyol composition with a polyisocyanate or a terminal isocyanate group-containing urethane prepolymer, and further includes the polymer polyol composition and / or the polyurethane resin. Examples thereof include a polyurethane resin obtained by reacting a polyurethane resin-forming composition containing a terminal polyol group-containing prepolymer obtained from a polymer polyol composition and a polyisocyanate.

  The polymer polyol composition of the present invention can form a urethane resin in the same manner as a normal polyol. This polymer polyol composition is mixed with a polyisocyanate compound having two or more isocyanate groups in one molecule, such as a terminal isocyanate group-containing urethane prepolymer obtained from a polyisocyanate and / or an active hydrogen compound component and an equivalent or more polyisocyanate. If necessary, it is heated to cure and form a urethane resin. At this time, if necessary, a urethanization catalyst may be used.

Moreover, after once producing a urethane resin-forming composition, a curing reaction can be performed to form a urethane resin. The urethane resin-forming composition using the present polymer polyol composition can be selected variously depending on the application, as in the case of using ordinary polyols, and examples thereof include the following forms.
(1) The polymer polyol composition of the present invention is used as an active hydrogen compound component, and a polyisocyanate and / or a polyol (the aforementioned low molecular polyol, polyether polyol, castor oil fatty acid ester polyol, and polyester polyol, polycarbonate polyol, polyolefin described later) A two-component urethane resin-forming composition comprising an isocyanate group-terminated urethane prepolymer obtained by reacting a polyol or the like with an equivalent or more polyisocyanate as an isocyanate component.
(2) The polymer polyol composition of the present invention is reacted with an equivalent amount or more of polyisocyanate to obtain an isocyanate-terminated urethane prepolymer as an isocyanate component. A polyol (the aforementioned low-molecular polyol, polyether polyol, castor oil fatty acid ester polyol and Polyester polyol, polycarbonate polyol, polyolefin polyol, etc., which will be described later), polyamine, water and the like, a two-component urethane resin-forming composition comprising an active hydrogen compound component.
(3) Two liquids using the polymer polyol composition of the present invention as an isocyanate component by reacting the polymer polyol composition of the present invention with an equivalent or more polyisocyanate to obtain an isocyanate-terminated urethane prepolymer. Type urethane resin-forming composition.
(4) Using the polymer polyol composition of the present invention as an active hydrogen compound component, blocked polyisocyanate (isocyanate group-terminated urethane prepolymer obtained by reacting polyisocyanate and / or polyol with an equivalent amount or more of polyisocyanate, methyl ethyl ketone oxime, A one-component urethane-resin-forming composition comprising an isocyanate component as a component obtained by reacting with ε caprolactam, dicyclohexylamine, phenols and the like to block an isocyanate group.
(5) A one-component moisture-curable urethane resin-forming composition obtained by reacting the polymer polyol composition of the present invention with an equivalent or more polyisocyanate to form an isocyanate-terminated urethane polymer.

  In the case of a two-component urethane resin-forming composition, the method for curing the urethane resin-forming composition is to mix an active hydrogen component and an isocyanate component, and if necessary, heat and cure. In the case of a one-component urethane resin-forming composition using a blocked isocyanate, the blocking agent is dissociated and cured by heating. In the case of a one-component moisture-curable urethane resin-forming composition, it is heated as necessary and cured by moisture.

  A usual urethanization catalyst can be used if necessary for the formation and production of the urethane resin. For example, tin-based catalysts (such as dibutyltin dilaurate), titanium-based catalysts (such as tetrabutyl titanate), bismuth-based catalysts (such as bismuth octylate), amine-based catalysts (such as triethylenediamine, N-ethylmorpholine, diethylethanol) Amine, N, N, N ′, N′-tetramethylhexamethylenediamine, tetramethylethylenediamine, bis-2-dimethylaminoethyl ether, 1,2-dimethylimidazole, 1-methylimidazole, 1-isobutyl-2-methyl And imidazole, 1,8-diazabicyclo- [5,4,0] -undecene-7) and the like. The urethanization catalyst can be added in advance to the isocyanate component and the active hydrogen component, or can be added separately at the time of curing.

  In the urethane resin and urethane resin-forming composition using the polymer polyol composition of the present invention, the polymer polyol composition can be used alone or in combination with other polyols. When used in combination with other polyols, from the viewpoint of imparting water resistance, oxidation stability, and resin strength to the urethane resin, the proportion of the polymer polyol composition of the present invention in the total polyol used is usually 20% or more, preferably 30. % Or more, particularly preferably 50% or more.

  Examples of the polyol that can be used in combination with the polymer polyol composition of the present invention include a low-molecular-weight polyol, a polyether polyol, and a castor oil fatty acid ester-based polyol together with a vinyl monomer in a polyester polyol, a polycarbonate polyol, a polyolefin polyol, and a polyether polyol. Examples include polymer polyols obtained by polymerization.

  Polyester polyols include polycarboxylic acids [aliphatic saturated or unsaturated polycarboxylic acids (C2-40, such as adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, dimerized linoleic acid), aromatic A linear or branched polyester polyol formed from a polycarboxylic acid (C8-15, such as phthalic acid, isophthalic acid, etc.) and a polyol (the aforementioned low molecular polyol and / or polyether polyol); a polylactone polyol [ For example, one or more of the low molecular polyols (2 to 3 valences) is used as an initiator, and (substituted) caprolactone (C6-10, for example, ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl- ε-Caprolactone) as catalyst (organometallic compound, metal chelate compound, fat Polyester polyol (for example, polycaprolactone polyol) subjected to addition polymerization in the presence of a fatty acid metal acylate, etc.]; Addition of alkylene oxide (ethylene oxide, propylene oxide, etc.) to a polyester having a carboxyl group and / or OH group at the terminal Examples include polyether ester polyols obtained by polymerization; polycarbonate polyols and the like.

  Examples of the polycarbonate polyol include those obtained by reacting the aforementioned low molecular weight polyol with a dialkyl carbonate such as ethylene carbonate and diethyl carbonate and a diaryl carbonate such as diphenyl carbonate.

  Examples of the polyolefin polyol include a hydroxyl group-containing polybutadiene, a hydrogenated hydroxyl group-containing polybutadiene, a hydroxyl group-containing polyisoprene, a hydrogenated hydroxyl group-containing polyisoprene, and a hydroxyl group-containing styrene butadiene copolymer.

  Examples of the polymer polyol obtained by polymerizing a vinyl monomer in a polyether polyol include those described in Patent Documents 1 and 2 described above.

  The polyisocyanate is a compound having 2 to 3 or more isocyanate groups in one molecule. Examples of the polyisocyanate include C (in the case of polyisocyanate, carbon atoms excluding carbon atoms in the isocyanate group). 2 to 18 aliphatic polyisocyanates, C4 to 15 alicyclic polyisocyanates, C6 to 20 aromatic polyisocyanates, C8 to 15 araliphatic polyisocyanates, isocyanates of these polyisocyanates Examples thereof include compounds obtained by modifying some or all of the groups isocyanurate, burette, allophanate, uretdione, uretonimine, carbodiimide, oxazolidone, amide or imide, and mixtures thereof.

  Examples of the aliphatic polyisocyanate include diisocyanate [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methylcaproate, Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, etc.], triisocyanate [1,6,11-undecane triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.] Is mentioned.

  Examples of alicyclic polyisocyanates include diisocyanates [isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, etc.]. Can be mentioned.

  Examples of the aromatic polyisocyanate include diisocyanate [2,4- and / or 2,6-toluene diisocyanate, 4,4′-, 2,4′- and / or 2,2′-diphenylmethane diisocyanate, naphthalene diisocyanate, etc. And those having 3 or more isocyanate groups [polymethylene polyphenyl polyisocyanate having 3 or more benzene rings].

  Examples of the araliphatic polyisocyanate include diisocyanate [xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, diisocyanate ethylbenzene, and the like].

  Additives used in ordinary polyurethane resins when using this polymer polyol composition to produce urethane resins, ie, foaming agents, flame retardants, fillers, hydrolysis inhibitors, antioxidants, UV absorbers Antifoaming agents such as antifungal agents, mold release agents, dehydrating agents, carbon dioxide gas absorbents, and the like can be used. These additives can also be added to the urethane resin-forming composition using the present polymer polyol composition.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. Hereinafter, the part means part by weight.

The composition of the following raw materials, manufacturers, etc. used in the following production examples and examples are as follows.
MDI: Diphenylmethane diisocyanate (Millionate MT; manufactured by Nippon Polyurethane Co., Ltd.)
TDI: Toluene diisocyanate (Coronate T-80; manufactured by Nippon Polyurethane Co., Ltd.)
Carbodiimide-modified MDI: Carbodiimide-modified diphenylmethane diisocyanate (Luprinate MM-103, NCO% = 29.5%; manufactured by BASF INOAC Polyurethane Co., Ltd.)
Partially dehydrated castor oil: hydroxyl value 120 mgKOH / g, TOYOACE P-110F; manufactured by Tokaken Co., Ltd. Castor oil: hydroxyl value 161 mgKOH / g, castor oil SL; manufactured by Ito Oil Co., Ltd. HEMA: hydroxyethyl methacrylate (acrylic) Estel HO, manufactured by Mitsubishi Rayon Co., Ltd.)
AMBN: 2,2′-azobis (2-methylbutyronitrile) (V-59; manufactured by Wako Pure Chemical Industries, Ltd.)
HPEDA: N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine

Production Examples 1-2: Production of Dispersant <Production Example 1> Production of Dispersant (D-1) 144 parts of methyl ethyl ketone was charged into a 1 L four-necked flask equipped with a temperature controller, a stirring blade and a dropping funnel. Add 150 parts (1.2 equivalents) of MDI and dissolve. Further, 374 parts (0.8 equivalent) of partially dehydrated castor oil was added and stirred at 70 ° C. for 4 hours. The isocyanate group content (NCO%) of this product was 2.5. Further, 53 parts (0.4 equivalent) of HEMA was added, and the mixture was further reacted at 70 ° C. for 6 hours. It was confirmed that NCO% was 0.01% or less by a titration method, and it was designated as Dispersant (D-1).

<Production Example 2> Production of Dispersant (D-2) In a 500 mL four-necked flask equipped with a temperature controller, a stirring blade and a dropping funnel, 28 parts (0.16 mol) of TDI and tetrabutyl titanate were added. 0.01 part was added, the temperature was adjusted to 30 ° C., and then 9 parts (0.07 mol) of HEMA was added dropwise over 2 hours. Meanwhile, the reaction temperature was kept at 40-50 ° C. PO was added to pentaerythritol, which had been put in a 1 L capacity four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel in advance, and then EO was added. The mixture was placed in 963 parts (0.14 mol) of a polyol having a hydroxyl group equivalent of 1750 and stirred at a reaction temperature of 80 to 90 ° C. for 4 hours. It confirmed that NCO% was 0.01% or less by the titration method, and it was set as the dispersing agent (D-2). The hydroxyl value of (D-2) was 20 mgKOH / g, and the viscosity was 20000 mPa · s / 25 ° C.

Examples 1-3: Manufacture of polymer polyol composition <Example 1> Manufacture of polymer polyol composition (POP-1) A temperature controller, a stirring blade, a dripping pump, a pressure reducing device, a cooling pipe, a nitrogen inflow and an outlet are provided. 200 parts of castor oil was added to a 1 L four-necked flask equipped, and nitrogen gas was flowed at 1 L / min for 30 minutes, and the space was replaced with nitrogen gas. While flowing a small amount of nitrogen gas, the temperature was raised to 125 ° C. with stirring. A mixture of castor oil 200 parts, HEMA 160 parts, styrene 40 parts, dispersant (D-1) 20 parts, AMBN 4 parts and xylene 20 parts was continuously injected over 3 hours at 125 ° C. with stirring. Further, a mixture of 4 parts of AMBN and 20 parts of xylene solution was added over 2 hours. After the addition, the mixture was further stirred for 1 hour, and then the pressure was gradually reduced to 100 Pa, and xylene and unreacted styrene were stripped for 3 hours to obtain a polymer polyol composition 1 (POP-1).

<Example 2> Production of polymer polyol composition (POP-2) Using the same apparatus as in Example 1, castor oil 200 parts, HEMA 160 parts, styrene 40 parts, dispersant (D-1) 20 parts, AMBN 4 parts Example 1 except that 200 parts of castor oil, 160 parts of acrylonitrile, 40 parts of styrene, 10 parts of dispersant (D-2), 4 parts of AMBN and 20 parts of xylene solution were added instead of the mixture of 20 parts of xylene solution and xylene solution. The same operation as 1 was performed to obtain a polymer polyol composition 2 (POP-2).

<Example 3> Production of polymer polyol composition (POP-3) Using the same apparatus as in Example 1, castor oil 200 parts, HEMA 160 parts, styrene 40 parts, dispersant (D-1) 20 parts, AMBN 4 parts 200 parts castor oil, 100 parts acrylonitrile, 100 parts styrene, 2 parts divinylbenzene, 10 parts dispersant (D-2), 4 parts AMBN, 20 parts xylene, and a non-reactive dispersant The same procedure as in Example 1 was conducted except that 4 parts of a propylene oxide adduct of bisphenol A (hydroxyl value 211 mgKOH / g) was added to obtain a polymer polyol composition 3 (POP-3).

Comparative Example 1: Production of Comparative Polymer Polyol Composition <Comparative Example 1> Production of Comparative Polymer Polyol Composition (POP-Comparative) In the same apparatus as in Example 1, instead of castor oil, propylene oxide-ethylene oxide instead of glycerin -Propylene oxide was added in the same order as in Example 1 except that a polyol having a hydroxyl value of 56 mgKOH / g and an ethylene oxide content of 9% (Sanix GP-3030; manufactured by Sanyo Chemical Industries, Ltd.) was used. The polymer polyol comparative example (POP-comparison) was obtained.

The analysis method of the synthesized polymer polyol composition is as follows.
<Volume average particle diameter of polymer fine particles>
2 mg of the polymer polyol composition is added to 30 ml of castor oil, and the mixture is stirred and uniformly dispersed with a magnetic stirrer for 3 minutes. The sample was immediately put into a measurement cell, and the volume average particle size was measured by a dynamic light scattering method using a laser diffraction / scattering particle size distribution analyzer (LA-750; manufactured by Horiba, Ltd.).

<Viscosity>
The polymer polyol composition temperature-controlled at 25 ° C. was measured with a rotary B-type viscometer (RB-80L; manufactured by Toki Sangyo Co., Ltd.).

<Polymer particle content>
Weigh the 50 ml centrifuge tube and 100 ml eggplant flask to 3 decimal places (W1 and W2 respectively). About 5 g of polymer polyol is added to the centrifuge tube and precisely weighed (W3). And Add 15 ml of acetone / hexane = 2/8 mixed solvent and shake. 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. Transfer the supernatant to the eggplant flask using a glass pipette. The residual sediment is diluted by adding 15 ml of a mixed solvent of acetone / hexane = 2/8, and the operation of centrifuging and removing the supernatant in the same manner as described above is repeated three more times. The centrifuge tube containing the residual sediment is dried under reduced pressure at 60 ° C. for 60 minutes at 2,666-3,999 Pa (20-30 torr) in a vacuum dryer, and the weight after drying is measured (W4). Let dry matter be a polymer particle part. On the other hand, the eggplant flask was set in an evaporator, and volatile components were removed at 60 ° C. and 2,666 to 3,999 Pa (20 to 30 torr) until almost no distillation was performed. The dried solution is dried under reduced pressure at 3,999 Pa (20-30 torr) at 60 ° C. for 60 minutes, and the weight after drying is measured (W5). The obtained solution is used as a dispersion medium phase. The value calculated by the following formula (A) is taken as the polymer particle content.
Polymer particle content (% by weight) = (W4-W1) × 100 / (W3-W1) (A)
Further, the value calculated by the following formula (B) is defined as the dispersed phase content, and it is confirmed that the sum of the polymer particle content and the dispersion medium phase content is within 100 ± 1.5. If the sum is outside this range, repeat the experiment.
Dispersion medium phase content (% by weight) = (W5-W2) × 100 / (W3-W1) (B)

<Hydroxyl value of dispersion medium phase>
The hydroxyl value of the dispersion medium phase obtained by the above operation was measured by the following method.
About 2 g of the dispersion medium phase is accurately weighed (Sg) in a 300 ml Erlenmeyer flask, and 25 ml of phthalic anhydride / pyridine solution (42 g of phthalic anhydride dissolved in 300 ml of pyridine) is added. Attach a cooling tube, put in a 120 ° C. oil bath, and react for 1 hour. After the reaction, the Erlenmeyer flask is put on an oil bath and allowed to cool for 5 minutes. Then, 10 ml of high-purity water is added and shaken from the upper part of the condenser, and the mixture is further left for 5 minutes. Remove the Erlenmeyer flask from the oil bath, cool to room temperature, and then remove the cooling tube. 0.5 ml of phenolphthalein indicator is added, titrated with 0.5 mol / l potassium hydroxide solution, and the end point is the point where the slight red color lasts for 30 seconds. Perform a blank test at the same time. The hydroxyl value is calculated by the following formula.
Hydroxyl value = (BA) × f × 28.05 / S
B: Drop constant of 0.5 mol / l potassium hydroxide solution required for the blank test (ml)
A: Drop constant (ml) of 0.5 mol / l potassium hydroxide solution required for the test
f; Potency of 0.5 mol / l potassium hydroxide solution S; Weight of sample (g)
Table 1 shows analytical values of the polymer polyol composition.

Production Examples 3 to 5: Production of Isocyanate Component <Production Example 3> Production of Isocyanate Component (IS-1) In a 1 L four-necked flask equipped with a temperature controller, stirring blade, cooling pipe, nitrogen inlet and outlet While flowing a small amount of nitrogen gas, 200 parts of MDI and 170 parts of castor oil were added and reacted at 60 ° C. for 3 hours. Furthermore, 100 parts of carbodiimide-modified MDI was added and stirred for 30 minutes to obtain isocyanate component 1 (IS-1). (IS-1) had an NCO% of 16.2% and a viscosity of 3100 mPa · s.

<Manufacture example 4> Manufacture of isocyanate component (IS-2) While flowing a small amount of nitrogen gas into a 1 L capacity four-necked flask equipped with a temperature controller, stirring blade, cooling pipe, nitrogen inflow and outlet, MDI250 And 150 parts of (POP-1) produced in Example 1 were added and reacted at 60 ° C. for 3 hours. Furthermore, 100 parts of carbodiimide-modified MDI was added and stirred for 30 minutes to obtain isocyanate component 2 (IS-2). (IS-2) had an NCO% of 16.2% and a viscosity of 2100 mPa · s.

<Manufacture example 5> Manufacture of isocyanate component (IS-3) MDI238 while flowing a small amount of nitrogen gas into a 1 L four-necked flask equipped with a temperature controller, a stirring blade, a condenser, a nitrogen inflow and an outlet Part and 232 parts of (POP-3) produced in Example 3 were added and reacted at 60 ° C. for 3 hours. Furthermore, 106 parts of carbodiimide-modified MDI was added and stirred for 30 minutes to obtain isocyanate component 3 (IS-3). (IS-3) had an NCO% of 16.2% and a viscosity of 2100 mPa · s.

Production Examples 6 to 9: Preparation of Active Hydrogen Compound Component <Production Example 6> Active Hydrogen Compound Component (OH-1)
Add 400 parts of castor oil and 50 parts of HPEDA to a 1 L four-necked flask equipped with a temperature controller, stirring blade, cooling pipe, nitrogen inlet and outlet, while stirring a small amount of nitrogen gas. A hydrogen compound component (OH-1) was obtained. The hydroxyl value of (OH-1) was 228 mgKOH / g, and the viscosity was 850 mPa · s.

<Production Example 7> Active hydrogen compound component (OH-2)
In the same apparatus as in Production Example 6, the same operation as in Production Example 6 was carried out except that 400 parts of (POP-1) was added instead of 400 parts of castor oil to obtain an active hydrogen compound component (OH-2). . The hydroxyl value of (OH-2) was 179 mgKOH / g, and the viscosity was 4500 mPa · s.

<Production Example 8> Active hydrogen compound component (OH-3)
In the same apparatus as in Production Example 6, instead of 400 parts castor oil and 50 parts HPEDA, 400 parts (POP-2), 50 parts HPDA, and propylene oxide adduct of glycerin (Sanix GP-250, hydroxyl value 672 mgKOH / g, Sanyo Except for adding 30 parts of Kasei Kogyo Co., Ltd., the same operation as in Production Example 6 was performed to obtain an active hydrogen compound component (OH-3). The hydroxyl value of (OH-3) was 210 mgKOH / g, and the viscosity was 2300 mPa · s.

<Production Example 9> Active hydrogen compound component (OH-4)
In the same apparatus as in Production Example 6, instead of 400 parts of castor oil and 50 parts of HPEDA, 400 parts of (POP-3), 40 parts of HPEDA, and a propylene oxide adduct of glycerin (Sanix GP-250, hydroxyl value 672 mgKOH / g, Sanyo Except for adding 40 parts of Kasei Kogyo Co., Ltd., the same operation as in Production Example 6 was performed to obtain an active hydrogen compound component (OH-4). The hydroxyl value of (OH-4) was 210 mgKOH / g, and the viscosity was 2300 mPa · s.

  Examples 4 to 8 and Comparative Examples 2 to 3 of the urethane resin-forming composition in which the isocyanate component and the active hydrogen compound component prepared above are combined are shown in Table 2.

In order to evaluate the performance of the urethane resin of the present invention, a urethane resin cured product was obtained by the following method.
Urethane resin cured products Examples 4 to 8 and Comparative Examples 2 to 3 were prepared by combining the isocyanate component and the active hydrogen compound component of the urethane resin-forming composition shown in Table 2 with the following method.

  The isocyanate component and the active hydrogen compound component were each degassed under reduced pressure (1000 Pa × 2 hours) at 25 ° C. A total of 100 parts were weighed at the blending ratios in Table 2, and stirred and mixed with a rotary stirrer (rotation speed: 300 rpm) for 30 seconds. The mixed solution is centrifuged and defoamed at 3500 rpm for 30 seconds using a centrifuge (H103N type, manufactured by Kokusan Co., Ltd.), and then placed in a SUS container having a height of 120 mm, a width of 120 mm, and a height of 10 mm so that the height becomes 1 mm. In addition, it was cured for 48 hours in a thermostatic bath at 50 ° C. to obtain a cured urethane resin.

  In addition, Example 9 of the urethane resin hardened | cured material in Table-3 is an example created not from making a urethane resin formation composition but directly from polyisocyanate and a polyol as follows.

Example 9:
Carbodiimide-modified MDI, POP-3 and HPEDA were each degassed under reduced pressure (1000 Pa × 2 hours) at 25 ° C. Carbodiimide-modified MDI, POP-3 and HPEDA were weighed in a total of 100 parts at a blending ratio of 31: 66: 2, and thereafter the same operation was performed to obtain Example 9 of a urethane resin cured product.

<Storage elastic modulus of cured urethane resin>
In order to evaluate heat resistance, the storage elastic modulus was measured by the following method. The urethane resin cured product was cut into a rectangular shape having a length of 20 mm and a width of 5 mm, and the storage elastic modulus was measured at 10 Hz using a dynamic viscoelasticity measuring device (Rheogel-E4000; manufactured by UBM). Table 3 shows the storage elastic modulus at 25 ° C and 80 ° C. The storage elastic moduli of Examples 4 to 9 and Comparative Example 3 have small differences at 25 ° C. and 80 ° C., both of which are in the range of 80 to 100 MPa, indicating that the heat resistance is good. In Comparative Example 2, 25 ° C. is 320 MPa, but 80 ° C. is significantly reduced to 6.5 MPa, and the heat resistance is poor.

<Hydrolysis resistance and oxidation stability test>
The urethane resin cured product was punched into a No. 3 dumbbell defined in JIS K7312 (physical test method for thermosetting urethane elastomer moldings) to obtain a test piece. The test piece was immersed in 1N NaOH aqueous solution at 40 ° C. for 30 days to conduct a hydrolysis resistance test. Similarly, the test piece was immersed in a hypochlorous acid aqueous solution having a chlorine concentration of 5000 ppm at 40 ° C. for 30 days to conduct an oxidation stability test. A tensile tester (manufactured by Shimadzu Corporation) was used for each of five test pieces before and after the test, and a tensile test was performed at 23 ° C. and a tensile speed of 500 mm / min to measure the tensile strength. The average value of three intermediate values excluding the highest value and the lowest value was taken as the measured value, and the values before and after the test were compared. The results are shown in Table-3. Examples 4 to 9 are excellent in both hydrolysis resistance and oxidation stability. Comparative Example 2 is excellent in oxidation stability but slightly inferior in hydrolysis resistance. Comparative Example 3 is poor in both hydrolysis resistance and oxidation stability.

  The polymer polyol composition for polyurethane resin and the polyurethane resin-forming composition of the present invention are used for the production of polyurethane resins such as polyurethane foam, polyurethane elastomer, polyurethane adhesive, polyurethane encapsulant, and the like. Oxidation stability and heat resistance can be imparted. In particular, it is suitable for the production of water treatment film adhesives, sealants, and electrical sealants where these properties are important.

Claims (9)

  A polymer polyol composition for urethane resin, comprising a dispersion medium containing a castor oil fatty acid ester-based polyol, and polymer fine particles dispersed in the dispersion medium.   Castor oil fatty acid ester-based polyol is castor oil, hydrogenated castor oil, partially dehydrated castor oil, a low molecular polyol having a molecular weight of 60 to 300 or a polyether polyol having a number average molecular weight of 100 to 2000 and castor oil or hydrogenated castor oil. 2. The polymer polyol composition for urethane resin according to claim 1, which is at least one selected from the group consisting of compounds obtained by ester exchange reaction or esterification reaction with castor oil fatty acid or hydrogenated castor oil fatty acid.   The polymer polyol composition for urethane resin according to claim 1 or 2, wherein the polymer fine particles are fine particles made of a polymer of a vinyl monomer.   The polymer polyol composition for urethane resin according to any one of claims 1 to 3, wherein the polymer fine particles have a volume average particle size of 0.01 to 60 µm.   The polymer polyol composition for urethane resin according to any one of claims 1 to 4, comprising 20 to 70% by weight of the polymer fine particles based on the total weight of the dispersion medium and the polymer fine particles.   The polymer polyol composition for urethane resins according to any one of claims 1 to 5, obtained by polymerizing the vinyl monomer in the dispersion medium.   A polyurethane resin obtained by reacting the polymer polyol composition according to claim 1 with a polyisocyanate and / or terminal isocyanate group-containing urethane prepolymer.   A polyurethane resin-forming composition comprising the polymer polyol composition according to any one of claims 1 to 6 and / or a terminal isocyanate group-containing prepolymer obtained from the polymer polyol composition and a polyisocyanate.   A polyurethane resin obtained by reacting the polyurethane resin-forming composition according to claim 8.