Polyol composition

Abstract

To provide a polyol composition having excellent storage stability and dispersion stability, and excellent handleability, and containing polyvinyl chloride-based crosslinked copolymer particles dispersed therein, the polyol composition suitable for polyurethane-forming material.SOLUTION: A polyol composition comprises polyvinyl chloride-based copolymer particles dispersed as solid in polyols, wherein the particles have an average particle size of 0.1-1.5 μm and include crosslinked structures including 0.1-1.0 wt.% of polyfunctional monomer residue units having two or more ethylenic double bonds in each molecule, with the solid content of 10-45 wt.%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol composition containing vinyl chloride-based crosslinked copolymer particles, and particularly relates to a polyol composition in which vinyl chloride-based crosslinked copolymer particles are dispersed, which is excellent in storage stability and dispersion stability, has good handling performance, and is suitable as a polyurethane-forming material.

Background Art

[0002] Conventionally, as a method for making polyurethane flame-retardant, a method using a polyol containing polyvinyl chloride particles as its raw material has been proposed. For example, a polyol dispersion in which polyvinyl chloride particles of 1 to 50 μm are dispersed (see, for example, Patent Document 1), a method using polyvinyl chloride particles and a carbonyl group-containing compound as a stabilizer (see, for example, Patent Document 2), a method for preparing a polyol in which vinyl chloride monomers are polymerized in a polyol to disperse polyvinyl chloride particles (see, for example, Patent Document 3), etc. have been proposed.

[0003] Also, for improving dispersion stability, for example, a vinyl chloride polymer latex having a volume average particle diameter of 0.2 to 2 μm containing a vinyl chloride polymer, a phosphate ester or a phosphate ester salt (see, for example, Patent Document 4), etc. have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the proposals in Patent Documents 1 to 3 had problems with the dispersibility and stability of polyvinyl chloride particles in polyols. Furthermore, the vinyl chloride polymer latex proposed in Patent Document 4 concerns latex itself, which has excellent dispersion stability, and does not address dispersion stability in polyol compositions.

[0006] Therefore, there is a need for a polyol composition that offers excellent storage stability and dispersion stability of polyvinyl chloride particles. [Means for solving the problem]

[0007] As a result of diligent research into the above-mentioned problems, the inventors of the present invention have found that a polyol composition obtained by dispersing vinyl chloride copolymer particles having a crosslinked structure in a polyol exhibits excellent storage stability and dispersion stability, making it suitable as a polyurethane raw material, and have completed the present invention.

[0008] In other words, the present invention relates to a polyol composition characterized by dispersing vinyl chloride copolymer particles having a crosslinked structure containing 0.1 to 1.0% by weight of polyfunctional monomer residue units having two or more ethylenically double bonds in the molecule and an average particle diameter of 0.1 to 1.5 μm, as solid content, in a polyol, and having a solid content concentration of 10 to 45% by weight.

[0009] The present invention will be described in detail below.

[0010] The polyol composition of the present invention comprises a polyol in which vinyl chloride copolymer particles having a crosslinked structure with an average particle diameter of 0.1 to 1.5 μm are dispersed as solid content, wherein the vinyl chloride copolymer particles having a crosslinked structure contain 0.1 to 1.0% by weight of polyfunctional monomer residue units having two or more ethylenically double bonds in the molecule.

[0011] The polyols constituting the polyol composition of the present invention may be any polyols belonging to the category known as polyols. Examples include conventionally known polyether polyols, polyester polyols, polymer polyols, polycarbonate polyols, and flame-retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used individually or mixed and used in combination as appropriate.

[0012] Polyether polyols are not particularly limited, and examples include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, which are compounds having at least two active hydrogen groups; amines such as ethylenediamine; and alkanolamines such as ethanolamine and diethanolamine, which are produced by addition reactions of these starting materials with alkylene oxides such as ethylene oxide and propylene oxide (see, for example, the method described in Gunter Oertel, "Polyurethane Handbook" (1985), Hanser Publishers (Germany), pp. 42-53).

[0013] Polyester polyols are not particularly limited and include, for example, those obtained from the reaction of dibasic acids and glycols, waste materials from nylon manufacturing, waste materials from trimethylolpropane and pentaerythritol, waste materials from phthalate polyesters, and polyester polyols derived from processed waste materials (see, for example, Keiji Iwata, "Polyurethane Resin Handbook" (1987), Nikkan Kogyo Shimbun, p. 117).

[0014] The polymer polyol is not particularly limited, and examples include polymer polyols obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, or styrene in the presence of a radical polymerization catalyst.

[0015] Flame-retardant polyols are not particularly limited and include, for example, phosphorus-containing polyols obtained by adding alkylene oxide to a phosphoric acid compound, halogen-containing polyols and phenolic polyols obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide.

[0016] Examples of commercially available polyols include (product name) Sannix (manufactured by Sanyo Chemical Industries, Ltd.), (product name) Exenol (manufactured by Asahi Glass Co., Ltd.), (product name) Actcol (manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), and (product name) VORANOL (manufactured by Dow).

[0017] Among these polyols, it is preferable that the average hydroxyl value is in the range of 20 to 1000 mgKOH / g. In particular, when used as a raw material for manufacturing flexible polyurethane or semi-rigid polyurethane, it is preferable that the average hydroxyl value is in the range of 20 to 100 mgKOH / g, and when used as a raw material for manufacturing rigid polyurethane, it is preferable that the average hydroxyl value is in the range of 100 to 800 mgKOH / g.

[0018] The vinyl chloride crosslinked copolymer particles constituting the polyol composition of the present invention are vinyl chloride copolymers having a crosslinked structure derived from polyfunctional monomer residue units having two or more ethylenically double bonds in the molecule, and any such copolymer may be used. By including vinyl chloride crosslinked copolymer particles as solid content in the polyol, a polyol composition is obtained that has excellent affinity with the polyol, excellent dispersibility and storage stability, and also possesses reactivity. If vinyl chloride polymer particles do not have a crosslinked structure, the resulting polyol composition will have poor dispersibility when the vinyl chloride polymer particles are concentrated at high concentrations. The content of polyfunctional monomer residue units having two or more ethylenically double bonds in the vinyl chloride crosslinked copolymer particles is preferably 0.1 to 1.0 wt%, as this is particularly excellent in dispersibility, storage stability, and reactivity. Here, if the concentration is less than 0.1 wt%, the resulting vinyl chloride copolymer particles will not exhibit the effects of the crosslinked structure when used in a polyol composition, and will have poor dispersibility at high concentrations. On the other hand, if the concentration of vinyl chloride crosslinked copolymer particles exceeds 1.0 wt%, the reaction system becomes unstable during production, making it difficult to stably produce the particles.

[0019] Furthermore, the vinyl chloride-based crosslinked copolymer particles have an average particle diameter of 0.2 to 1.2 μm, as having an average particle diameter of 0.1 to 1.5 μm results in extremely excellent mechanical strength. If the average particle diameter is less than 0.1 μm, the viscosity of the polyol composition becomes high, resulting in poor fluidity and processability. On the other hand, if the average particle diameter exceeds 1.5 μm, the polyol composition suffers from poor dispersibility and storage stability. As for methods for measuring the average particle diameter, for example, a method can be used to measure the particle diameter distribution using a disk centrifugal particle size distribution analyzer and determine the average particle diameter of the particles.

[0020] The vinyl chloride-based crosslinked copolymer particles can be prepared, for example, by copolymerizing a vinyl chloride-based monomer with a polyfunctional monomer having two or more ethylenically active double bonds in its molecule. The amount of polyfunctional monomer having two or more ethylenically active double bonds in its molecule should be such that vinyl chloride-based crosslinked copolymer particles with a polyfunctional monomer residue unit content of 0.1 to 1.0 wt% can be efficiently produced, and is preferably 0.1 to 1.0 wt%, with a preference for 0.1 to 0.8 wt% as this results in excellent dispersibility, storage stability, and reactivity. Examples of vinyl chloride monomers in this case include vinyl chloride monomers and copolymerizable monomers. Examples of polyfunctional monomers having two or more ethylenic double bonds in the molecule include triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, ethylene glycol divinyl ether, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diallyl phthalate, vinyl methacrylate, and vinyl crotate. These can be used individually or in combination of two or more.

[0021] As a method for producing the vinyl chloride crosslinked copolymer particles, any method that enables the production of the vinyl chloride crosslinked copolymer particles may be used. For example, a method of producing a vinyl chloride copolymer having a crosslinked structure by copolymerizing a vinyl chloride monomer with a polyfunctional monomer having two or more ethylenically double bonds in its molecule can be used. When producing the vinyl chloride crosslinked copolymer particles, polymerization initiators, emulsifiers, chain transfer agents, buffers, water-soluble initiators, reducing agents, etc., can be used as appropriate. These additives may, insofar as they achieve the objectives of the present invention, be included in the vinyl chloride crosslinked copolymer particles as solids in some cases.

[0022] As the polymerization initiator at that time, any initiator belonging to the category of polymerization initiators may be used. For example, water-soluble polymerization initiators such as potassium persulfate and ammonium persulfate; azo compounds such as azobisisobutyronitrile, peroxides such as lauroyl peroxide, t-butylperoxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate, and other oil-soluble polymerization initiators can be mentioned. Also, when performing the seed micro-suspension polymerization method, seed particles (seeds) containing an oil-soluble initiator may be used.

[0023] As the emulsifier, general anionic emulsifiers or nonionic emulsifiers can be mentioned. Examples of anionic emulsifiers include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate esters such as sodium lauryl sulfate and sodium tetradecyl sulfate; sulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate; fatty acid salts such as sodium laurate and potassium semi-hardened tallow fatty acid; ethoxysulfate salts such as sodium polyoxyethylene lauryl ether sulfate salt and sodium polyoxyethylene nonylphenyl ether sulfate salt; alkane sulfonates; sodium alkyl ether phosphate ester salts, etc. Examples of nonionic emulsifiers include polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, etc. Among them, since vinyl chloride-based crosslinked copolymer particles can be produced more stably, it is preferable to use an alkylbenzene sulfonate, an alkyl sulfate ester salt, or a mixture of an alkylbenzene sulfonate and an alkyl sulfate ester salt. Also, as the addition time of the emulsifier, it is only necessary for the emulsifier to be present during homogenization. It may be added all at once before or during homogenization, or a part may be added before or during homogenization, and the remaining emulsifier may be added intermittently or continuously during polymerization.

[0024] As the polymerization method in the manufacturing method, for example, vinyl chloride monomer, a polyfunctional monomer having two or more ethylenic double bonds in the molecule, an emulsifier, an oil-soluble polymerization initiator, and an emulsification aid such as a higher aliphatic alcohol as necessary are added to deionized water, mixed and dispersed with a homogenizer, etc., and then polymerization is carried out under gentle stirring, such as the micro-suspension polymerization method; the seed micro-suspension polymerization method carried out using seed particles (seeds) containing an oil-soluble polymerization initiator obtained by the micro-suspension polymerization method; the seed emulsion polymerization method in which emulsion polymerization is carried out using as seeds the particles obtained by the emulsion polymerization method in which a vinyl chloride-based monomer is polymerized under gentle stirring together with deionized water, an emulsifier, and a water-soluble polymerization initiator. At that time, for example, the polymerization temperature is set to 3~80°C, and it can be obtained as a latex in which the vinyl chloride-based crosslinked copolymer particles are dispersed.

[0025] Furthermore, the latex can be obtained as primary particles or aggregates thereof by spray drying. The aggregates can also be obtained as vinyl chloride crosslinked copolymer particles by grinding as needed. The dryer used to obtain vinyl chloride crosslinked copolymer particles can be a commonly used one, such as a spray dryer (for example, various spray dryers are shown in Figure 4.10 on page 121 of "SPRAY DRYING HANDBOOK" (by K. Masters, 3rd edition, 1979, published by Georgegodwin Limited)). There are no particular restrictions on the drying air inlet temperature and drying air outlet temperature, but a drying air inlet temperature of 80 to 200°C and a drying air outlet temperature of 45 to 75°C are commonly used, with a drying air inlet temperature of 100 to 170°C and a drying air outlet temperature of 50 to 70°C being even more preferable. The vinyl chloride crosslinked copolymer particles obtained after drying are primary particles or aggregates thereof that constitute latex, and are preferably in the form of granules of 10 to 100 μm. If the drying outlet temperature exceeds 55°C, it is preferable to pulverize the obtained vinyl chloride crosslinked copolymer from the viewpoint of dispersion when it is made into a polyol composition. If the drying outlet temperature is 55°C or lower, it is acceptable to use it in granular form or after pulverization. Furthermore, if the vinyl chloride crosslinked copolymer particles obtained by spray drying or the like are aggregates of primary particles, it is preferable that they are dispersed in the polyol and dispersed as primary particles when it is made into a polyol composition.

[0026] The polyol composition of the present invention has excellent workability and dispersibility, and therefore preferably has a viscosity of 10,000 mPa·s or less, particularly 1,000 to 9,500 mPa·s, and more preferably 1,000 to 8,000 mPa·s.

[0027] As a method for producing the polyol composition of the present invention, any method that enables the production of the polyol composition may be used. Examples include a method of mixing the vinyl chloride crosslinked copolymer particles with the polyol, a method of mixing a latex containing vinyl chloride crosslinked copolymer particles with the polyol, and then dehydrating the resulting mixture.

[0028] The polyol composition of the present invention has excellent dispersibility, storage stability, and reactivity, and can therefore be used as a raw material for polyurethanes, especially flame-retardant polyurethanes. For example, by blending it with isocyanate compounds such as aromatic polyisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate; and / or polyisocyanate compounds such as mixtures thereof, it can be used as a polyurethane-forming composition or polyurethane. [Effects of the Invention]

[0029] The polyol composition of the present invention exhibits excellent storage stability and dispersion stability, as well as good handling properties, making it suitable as a polyurethane forming material. [Examples]

[0030] The present invention will be described in more detail below with reference to examples, but the present invention is not to be limited in any way by these examples.

[0031] <Method for measuring the average particle size of vinyl chloride crosslinked copolymer particles> The particle size distribution of vinyl chloride crosslinked copolymer particles was determined by measuring the particle size distribution of vinyl chloride crosslinked copolymer particles obtained under conditions of a refractive index of 1.4 using a disk centrifugal particle size distribution analyzer (CPS Instruments, product name: CPS Disc Centrifuge), and then calculating the average particle size.

[0032] <Viscosity Measurement> Viscosity was measured using a Type B viscometer in accordance with JIS K-1557-5.

[0033] <Storage Stability Test> The storage stability test involved placing the polyol composition in a transparent glass bottle, leaving it at room temperature for one month, and visually inspecting for the presence or absence of sediment in the polyol composition.

[0034] Synthesis Example 1 1m 3 300 kg of deionized water, 300 kg of vinyl chloride monomer, 5.3 kg of lauroyl peroxide, and 18 kg of 25% by weight sodium dodecylbenzenesulfonate aqueous solution were charged into a stainless steel autoclave. Homogenization treatment was performed by circulating the mixture using a homogenizer for 3 hours, and then the temperature of the reaction system was raised to 45°C to start polymerization. After the pressure in the polymerization system decreased, the unreacted vinyl chloride monomer was recovered, and seed latex a was obtained with a solid content of 35% by weight, an average particle size of 0.55 μm, and containing 2% by weight of lauroyl peroxide as the polymer base.

[0035] Synthesis Example 2 1m 3 350 kg of deionized water, 300 kg of vinyl chloride monomer, 81 g of potassium persulfate, 10 kg of 16% by weight potassium laurate aqueous solution, and 20 kg of 25% by weight sodium dodecylbenzenesulfonate aqueous solution were charged into a stainless steel autoclave. The reaction system temperature was then raised to 54°C to start polymerization. After the polymerization system pressure decreased, the unreacted vinyl chloride monomer was recovered to obtain seed latex b with a solids content of 40% by weight and an average particle size of 0.15 μm.

[0036] Example 1 In a 2.5L stainless steel autoclave, 840g of deionized water, 720g of vinyl chloride monomer, 1.15g of diallyl phthalate, 8.6g of 5% by weight sodium dodecylbenzenesulfonate, 4.2 parts by weight of seed latex a obtained in Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer, and 1.5 parts by weight of seed latex b obtained in Synthesis Example 2 per 100 parts by weight of vinyl chloride monomer were charged. The temperature of this reaction mixture was raised to 45°C to start polymerization. From the start to the end of polymerization, 0.703 parts by weight of 5% by weight sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. Polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride monomer at 45°C to 0.461 MPa, and the unreacted vinyl chloride monomer and diallyl phthalate were recovered to obtain latex containing vinyl chloride crosslinked copolymer particles.

[0037] The obtained vinyl chloride crosslinked copolymer particles had an average primary particle size of 1.23 μm, and the content of diallyl phthalate residue units calculated from unreacted vinyl chloride monomer and diallyl phthalate was 0.16% by weight. The latex was then spray-dried in a spray dryer at a hot air inlet temperature of 158°C and an outlet temperature of 55°C to obtain aggregates of vinyl chloride crosslinked copolymer particles.

[0038] 350 g of the obtained vinyl chloride-based crosslinked copolymer particle aggregate and 650 g of glycerin-based polyether polyol ((trade name) Exenol EL-820, manufactured by AGC, OH value; 33KOH / g) were kneaded in a dissolver mixer to obtain a creamy polyol composition with a solid content of 35% by weight.

[0039] The resulting polyol composition contained dispersed vinyl chloride-based crosslinked copolymer particles with an average particle size of 1.23 μm, and its viscosity was 4100 mPa·s. A one-month storage stability test revealed no particle sedimentation, indicating a homogeneous state.

[0040] Example 2 200 g of the vinyl chloride-based crosslinked copolymer particle aggregate obtained in Example 1 and 800 g of glycerin-based polyether polyol ((trade name) Exenol EL-820, manufactured by AGC, OH value; 33KOH / g) were kneaded in a dissolver mixer to obtain a creamy polyol composition with a solid content of 20% by weight.

[0041] The resulting polyol composition contained dispersed vinyl chloride-based crosslinked copolymer particles with an average particle size of 1.23 μm, and its viscosity was 2200 mPa·s. A one-month storage stability test revealed no particle sedimentation, indicating a homogeneous state.

[0042] Example 3 In a 2.5L stainless steel autoclave, 600g of deionized water, 800g of vinyl chloride monomer, 4.0g of triallyl isocyanurate, 8.6g of 5% by weight sodium dodecylbenzenesulfonate, 4.5 parts by weight of seed latex a obtained in Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer, and 3.0 parts by weight of seed latex b obtained in Synthesis Example 2 per 100 parts by weight of vinyl chloride monomer were charged. The temperature of this reaction mixture was raised to 48°C to start polymerization. From the start to the end of polymerization, 0.703 parts by weight of 5% by weight sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. Polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride monomer at 48°C to 0.402 MPa, and the unreacted vinyl chloride monomer and triallyl isocyanurate were recovered to obtain latex of vinyl chloride copolymer particles having a crosslinked structure.

[0043] The obtained vinyl chloride crosslinked copolymer particles had an average primary particle size of 1.20 μm, and the content of triallyl isocyanerate residue units, calculated from unreacted vinyl chloride monomer and triallyl isocyanurate, was 0.5% by weight. The latex was then spray-dried using a spray dryer at a hot air inlet temperature of 158°C and an outlet temperature of 55°C to obtain aggregates of vinyl chloride crosslinked copolymer particles.

[0044] 350 g of the obtained vinyl chloride-based crosslinked copolymer particle aggregate and 650 g of glycerin-based polyether polyol ((trade name) Exenol EL-820, manufactured by AGC, OH value; 33KOH / g) were kneaded in a dissolver mixer to obtain a creamy polyol composition with a solid content of 35% by weight.

[0045] The resulting polyol composition contained dispersed vinyl chloride-based crosslinked copolymer particles with an average particle size of 1.20 μm, and its viscosity was 3500 mPa·s. A one-month storage stability test revealed no particle sedimentation, indicating a homogeneous state.

[0046] Example 4 In a 2.5L stainless steel autoclave, 600g of deionized water, 800g of vinyl chloride monomer, 4.0g of triallyl isocyanurate, 8.6g of 5% by weight sodium dodecylbenzenesulfonate, and 4.5 parts by weight of seed latex a obtained in Synthesis Example 1 were charged per 100 parts by weight of vinyl chloride monomer. The temperature of this reaction mixture was raised to 48°C to start polymerization. From the start to the end of polymerization, 0.703 parts by weight of 5% by weight sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. Polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride monomer at 48°C to 0.402 MPa, and the unreacted vinyl chloride monomer and triallyl isocyanurate were recovered to obtain latex of vinyl chloride-based crosslinked copolymer particles.

[0047] The obtained vinyl chloride crosslinked copolymer particles had an average primary particle size of 1.30 μm, and the content of triallyl isocyanerate residue units, calculated from unreacted vinyl chloride monomer and triallyl isocyanurate, was 0.5% by weight. The latex was then spray-dried using a spray dryer at a hot air inlet temperature of 158°C and an outlet temperature of 55°C to obtain aggregates of vinyl chloride crosslinked copolymer particles.

[0048] 350 g of the obtained vinyl chloride-based crosslinked copolymer particle aggregate and 650 g of glycerin-based polyether polyol ((trade name) Exenol EL-820, manufactured by AGC, OH value; 33KOH / g) were kneaded in a dissolver mixer to obtain a creamy polyol composition with a solid content of 35% by weight.

[0049] The resulting polyol composition contained dispersed vinyl chloride-based crosslinked copolymer particles with an average particle size of 1.30 μm, and its viscosity was 5600 mPa·s. A one-month storage stability test revealed no particle sedimentation, indicating a homogeneous state.

[0050] Comparative Example 1 In a 2.5L stainless steel autoclave, 840g of deionized water, 720g of vinyl chloride monomer, 10.8g of diallyl phthalate, 8.6g of 5% by weight sodium dodecylbenzenesulfonate, 4.2 parts by weight of seed latex a obtained by Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer, and 1.5 parts by weight of seed latex b obtained by Synthesis Example 2 per 100 parts by weight of vinyl chloride monomer were charged. The temperature of this reaction mixture was raised to 45°C to attempt the production of vinyl chloride copolymer particles with a triallyl isocyanerate residue content of 1.5% by weight.

[0051] However, the reaction system became unstable during the polymerization reaction, making it impossible to obtain latex with normal vinyl chloride copolymer particles.

[0052] Comparative Example 2 50 g of the vinyl chloride-based crosslinked copolymer particle aggregate obtained in Example 1 and 950 g of glycerin-based polyether polyol ((trade name) Exenol EL-820, manufactured by AGC, OH value; 33KOH / g) were kneaded in a dissolver mixer to obtain a creamy polyol composition with a solid content of 5% by weight.

[0053] The resulting polyol composition contained dispersed vinyl chloride-based crosslinked copolymer particles with an average particle size of 1.23 μm, and its viscosity was 1000 mPa·s. A one-month storage stability test revealed particle sedimentation, indicating poor stability.

[0054] Comparative Example 3 500 g of the vinyl chloride-based crosslinked copolymer particle aggregate obtained in Example 1 and 500 g of glycerin-based polyether polyol ((trade name) Exenol EL-820, manufactured by AGC, OH value; 33KOH / g) were kneaded in a dissolver mixer to obtain a creamy polyol composition with a solid content of 50% by weight.

[0055] The resulting polyol composition contained dispersed vinyl chloride-based crosslinked copolymer particles with an average particle size of 1.23 μm, and its viscosity was high at 12,300 mPa·s, posing a challenge in terms of processability.

[0056] [Table 1] [Industrial applicability]

[0057] The polyol composition of the present invention has low sedimentation, excellent storage stability and dispersion stability, and good handling performance. Furthermore, since the polyol composition of the present invention can produce polyurethane resins with good dispersion stability, it is expected to be suitable for use in the polyurethane resin manufacturing industry.

Claims

1. A polyol composition characterized by comprising vinyl chloride copolymer particles having a crosslinked structure containing 0.1 to 1.0% by weight of polyfunctional monomer residue units having two or more ethylenically double bonds in the molecule and an average particle size of 0.1 to 1.5 μm, dispersed in a polyol, with a solid content concentration of 10 to 45% by weight.

2. The polyol composition according to claim 1, characterized in that its viscosity is 10,000 mPa·s or less.

3. The polyol composition according to claim 1 or 2, characterized in that the polyfunctional monomer residue units having two or more ethylenically double bonds in the molecule are triallyl isocyanurate residue units and / or diallyl phthalate residue units.

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