JP2014237793A - Polyol composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition which shows little sedimentation, has excellent storage stability and dispersion stability, and has good handleability, and to provide a method for producing the polyol composition which has decreased viscosity before dehydration, good handleability, and good dispersion stability.SOLUTION: Provided is a polyol composition comprising vinyl chloride polymer particles in an amount of 10 to 50 wt.%, the polymer particles having a volume average particle diameter ([MV] value) of 0.2 to 5 μm, where the vinyl chloride polymer particles contain therein at least one selected from organic compounds including sulfate ester salts and sulfosuccinic acid salts in an amount of 0.05 to 10 pts.wt. relative to 100 pts.wt. of the vinyl chloride polymer. Also provided is a method for producing the polyol composition comprising: mixing a latex solution containing vinyl chloride polymer particles having a volume average particle diameter ([MV] value) of 0.1 to 2 μm and a polyol, followed by dehydration of the polyol composition; and a method for producing a polyurethane resin using the polyol composition.

Description

  The present invention relates to a polyol composition, and more particularly to a polyol composition containing a specific emulsifier in which vinyl chloride polymer particles are dispersed. The polyol composition of the present invention is useful as a polyurethane raw material.

  Conventionally, as a method for flame-retarding polyurethane, a method using a polyol containing polyvinyl chloride particles as a raw material has been proposed. For example, Patent Document 1 discloses a polyol dispersion in which 1 to 50 μm polyvinyl chloride particles are dispersed. Patent Document 2 discloses a method using polyvinyl chloride particles and a carbonyl group-containing compound as a stabilizer. Patent Document 3 discloses a method for preparing a polyol in which a polyvinyl chloride monomer is polymerized in a polyol to disperse polyvinyl chloride particles.

  However, the conventionally known method using a polyol containing polyvinyl chloride particles has a high viscosity before dehydration and has a problem in handling performance.

  The present applicant previously described that a vinyl chloride polymer particle and / or a vinyl chloride-unsaturated vinyl copolymer particle having a volume average particle diameter ([MV] value) of 0.05 μm or more and 1 μm or less is dispersed in a polyol in a dispersed state. A polyol composition containing at least 50% by weight and less than 50% by weight is proposed (Patent Document 4), and a polyol composition with good storage stability and flame retardancy having a viscosity after dehydration of 10,000 mPa · s or less is disclosed. ing.

  However, the handling performance before dehydration is not disclosed, and the storage stability is still insufficient.

  Furthermore, since the operation | work which requires filtration generate | occur | produces, dispersion stability is requested | required and the solution means with favorable dispersion stability is shown (patent document 1, patent document 5).

  However, the dispersion stability was still insufficient.

JP-A-1-65160 JP-A-9-59341 Japanese Patent Laid-Open No. 3-97715 JP 2010-31169 A JP-A-5-59134

  The present invention has been made in view of the above-mentioned background art, and its purpose is to lower the viscosity before dehydration, thereby further improving handling performance and excellent in storage stability and dispersion stability. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that the volume average particle diameter ([MV] value) of vinyl chloride polymer particles containing a specific emulsifier is 0.2 to 5 μm, and the inclusion of the particles. When the ratio is 10 to 50% by weight, the storage stability and dispersion stability are excellent, the handling performance is good, and the volume average particle diameter ([MV] value) is 0.1 to 2 μm. It has been found that when a latex solution containing coalesced particles and a polyol are mixed, the viscosity before dehydration is lowered, the handling performance is improved, and the dispersion stability is further improved, and the present invention has been completed. That is, the present invention contains vinyl chloride polymer particles having a volume average particle size ([MV] value) of 0.2 to 5 μm in a polyol in an amount of 10 to 50% by weight, and the vinyl chloride polymer particles A polyol composition containing 0.05 to 10 parts by weight of at least one selected from organic compounds having a sulfate ester salt and a sulfosuccinate with respect to 100 parts by weight of a vinyl chloride polymer, and a method for producing the same And a method for producing a polyurethane resin using the same.

  Hereinafter, the present invention will be described in detail.

  The polyol composition of the present invention is a polyol composition in which vinyl chloride polymer particles are dispersed in a polyol, and the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles contained in the polyol is It is 0.2-5 micrometers, The content rate is 10-50 weight% with respect to a polyol composition.

  When the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles is smaller than 0.2 μm, not only the viscosity of the polyol composition is likely to increase, but also the vinyl chloride polymer particles are easily aggregated and stored. Stability decreases and handling performance deteriorates. When the volume average particle diameter ([MV] value) is larger than 5 μm, particles are likely to settle when stored for a long time. From the point which prevents sedimentation more and the point where handling performance is more favorable, 0.3-4.5 micrometers is preferable.

  If the content (concentration) of the vinyl chloride polymer particles is less than 10% by weight, the polyurethane foam hardness expected as an effect of adding the polyol may be insufficient. There is a possibility that the viscosity of the composition is remarkably increased and handling becomes difficult, and further, the improvement in hardness of the polyurethane foam expected as an effect of adding a polyol may be insufficient. In order to further improve the handling performance, 20 to 45% by weight is preferable.

  In the present invention, in order to confirm that the vinyl chloride polymer particles contained in the polyol are present, the polyol containing the vinyl chloride polymer particles is simply diluted with water, and the particle size distribution is measured.

  In the present invention, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles may be any particle size distribution measuring apparatus based on the generally known laser diffraction method and dynamic light scattering method. Measurement is possible even using an apparatus, and there is no particular limitation. For example, it can be measured with a particle size distribution measuring device such as a microtrack (trade name, manufactured by Nikkiso Co., Ltd.).

  The vinyl chloride polymer particles contain 0.05 to 10 parts by weight of at least one selected from organic compounds having a sulfate ester salt and a sulfosuccinate with respect to 100 parts by weight of the vinyl chloride polymer. By containing a specific amount of a specific emulsifier, the dispersion stability is improved. When the content is less than 0.05 parts by weight, aggregates are generated, and when the content exceeds 10 parts by weight, impurities increase. In order to further improve the dispersion stability, 1 to 8 parts by weight is preferable.

  Examples of the compound having a sulfate ester salt include sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, and the organic compound having a sulfosuccinate. , Disodium polyoxyethylene alkyl sulfosuccinate, disodium polyoxyethylene alkyl ether sulfosuccinate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene lauryl ether sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate, etc. Can be mentioned.

  In addition to the specific emulsifier (at least one selected from organic compounds having a sulfate ester salt and a sulfosuccinate), the vinyl chloride polymer particles may contain other emulsifiers. Examples of other emulsifiers include alkylbenzene sulfonates, alkyl naphthalene sulfonates, compounds having alkyl diphenyl ether disulfonates, and compounds having higher fatty acid salts. Examples of the compound having an alkylbenzene sulfonate include sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate, and examples of the compound having an alkylnaphthalenesulfonate include sodium alkylnaphthalenesulfonate and alkylnaphthalenesulfone. Examples of the compound having an alkyl diphenyl ether disulfonate include sodium alkyl diphenyl ether disulfonate, potassium alkyl diphenyl ether disulfonate, and the like. Examples of the compound having a higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali.

  The vinyl chloride polymer particles contained in the polyol composition of the present invention can be prepared by polymerizing a vinyl chloride monomer alone. The polymerization method is not particularly limited except that at least one selected from organic compounds having a sulfate ester salt and a sulfosuccinate as an emulsifier is used, and the volume average particle diameter of the vinyl chloride polymer particles produced ([[ As long as the MV] value is 0.1 to 2 μm, any method generally known as a method for producing vinyl chloride polymer particles can be used. For example, an emulsion polymerization method in which a vinyl chloride monomer is polymerized with gentle stirring with deionized water, an emulsifier (surfactant), and a water-soluble polymerization initiator, and particles obtained by the emulsion polymerization method are seeded. Seed emulsion polymerization method for emulsion polymerization, vinyl chloride monomer alone, deionized water, emulsifier (surfactant), if necessary emulsification aids such as higher alcohols, oil-soluble polymerization initiator homogenizer The micro-suspension polymerization method in which polymerization is performed with gentle stirring after mixing and dispersion, etc., and the seed micro-suspension polymerization method in which polymerization is performed using a seed containing an oil-soluble polymerization initiator obtained by the micro-suspension polymerization method Etc. Of these, the emulsion polymerization method is particularly preferred in the present invention. The amount of at least one selected from organic compounds having a sulfate ester salt and a sulfosuccinate is 0.05 to 10 parts by weight, preferably 1 to 7 parts by weight.

  Examples of the polyol used in the polyol composition of the present invention include conventionally known polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used alone or in combination as appropriate.

  The polyether polyol is not particularly limited. For example, a compound having at least two active hydrogen groups (polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine) Etc., alkanolamines such as ethanolamine, diethanolamine, etc.) are used as starting materials, and this is prepared by addition reaction of this with alkylene oxide (such as ethylene oxide and propylene oxide). (See, for example, the method described in Gunter Oertel, “Polyurethane Handbook” (1985) Hanser Publishers (Germany), p. 42-53).

  The polyester polyol is not particularly limited, but examples thereof include those obtained from the reaction of dibasic acid and glycol, wastes from the production of nylon, trimethylolpropane, pentaerythritol wastes, and phthalic polyester wastes. And polyester polyols obtained by treating waste products (see, for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. 117).

  The polymer polyol is not particularly limited. For example, a polymer obtained by reacting the polyether polyol with an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. A polyol etc. are mentioned.

  The flame retardant polyol is not particularly limited. For example, a phosphorus-containing polyol obtained by adding alkylene oxide to a phosphoric acid compound, a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, A phenol polyol etc. are mentioned.

  Specific examples of these polyols are Sanniks (trade name, manufactured by Sanyo Kasei Kogyo Co., Ltd.), Exenol (trade name, manufactured by Asahi Glass Co., Ltd.), Actol (trade name, Mitsui Chemicals Polyurethane). Co., Ltd.), VORANOL (trade name, manufactured by DOW) and the like.

  As these polyols, for example, those having an average hydroxyl value in the range of 20 to 1000 mgKOH / g can be used and are not particularly limited. However, when producing a flexible polyurethane resin or a semi-rigid polyurethane resin, the average hydroxyl value is not limited. In the range of 20 to 100 mgKOH / g, when producing a rigid polyurethane resin, those having an average hydroxyl value in the range of 100 to 800 mgKOH / g are preferably used.

  Since the polyol composition of the present invention can be easily mixed and dispersed, the viscosity before dehydration is preferably 100,000 mPa · s or less, and the viscosity after dehydration is preferably in order to improve handling. It is preferably 10,000 mPa · s or less.

  In the method for producing a polyol composition of the present invention, for example, a latex solution containing vinyl chloride polymer particles having a volume average particle size ([MV] value) of 0.1 to 2 μm and a polyol are mixed, and the resulting mixture is mixed. It is characterized by dehydration.

  In the present invention, by mixing a latex solution containing a vinyl chloride polymer particle having a volume average particle size ([MV] value) of 0.1 to 2 μm and a polyol, water, polyol, and vinyl chloride polymer particles are contained. A mixture is obtained. This mixture will be in a liquid, gel, or cream state depending on the type of polyol. When this mixture becomes a gel or cream, for example, if it is a laboratory, T.M. K. It is preferable to stir until a uniform state is obtained using a high-speed emulsification / dispersing machine such as Homodispa (trade name, manufactured by Primix Co., Ltd.). If the homogenization is insufficient, the vinyl chloride polymer particles may be aggregated in the subsequent dehydration step. Further, if the volume average particle size ([MV] value) is smaller than 0.1 μm, the viscosity before dehydration increases, and it becomes difficult to mix and disperse when uniform using a disperser. It becomes difficult and the handling performance is inferior. In order to make the handling performance better, 0.2 to 1 μm is preferable, and 0.2 to 0.6 μm is more preferable.

  The method for dehydrating the mixture is not particularly limited. For example, in the laboratory level, the mixture may be deaerated while applying heat at around 50 ° C. under reduced pressure. Even a gel-like or cream-like mixture becomes liquid as dehydration proceeds. As a specific dehydration method, dehydration by a rotary evaporator can be exemplified at a laboratory level. Moreover, the method etc. which use the stirrer corresponding to high-viscosity stirring and the evaporation pot which can be pressure-reduced are illustrated.

  In order to prevent the vinyl chloride polymer particles from aggregating, the temperature during dehydration is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. On the other hand, in order to further shorten the dehydration time, room temperature or higher is preferable, and a temperature of 40 ° C. or higher is more preferable.

  In the present invention, the amount of dehydration can be arbitrarily determined with respect to the use of the polyol composition of the present invention, and is not particularly limited. For example, when a polyurethane resin is prepared, water is used as a foaming agent. Is used, it may be dehydrated so that the water content is 0 to 5% by weight, preferably 0 to 3% by weight.

  Next, the manufacturing method of the polyurethane resin using the polyol composition of this invention is demonstrated.

  The method for producing a polyurethane resin of the present invention is a method for producing a polyurethane resin in which a polyol component and a polyisocyanate component are reacted in the presence of a catalyst, and the above-described polyol composition of the present invention is used as a part of the polyol component. The feature is to do.

  In the method for producing a polyurethane resin of the present invention, the polyol used as the polyol component is the above-described polyol composition of the present invention. However, the above-described conventionally known polyether polyols and polyesters are within the scope of the present invention. Polyols such as polyols, polymer polyols and flame retardant polyols can be used. These polyols can be used alone or in combination as appropriate.

  In the method for producing a polyurethane resin of the present invention, in order to further improve the hardness of the polyurethane foam expected as an effect of adding a polyol, chlorination with respect to the polyol used (including the polyol in the polyol composition of the present invention). The content of the vinyl polymer particles is preferably 10% by weight or more, and more preferably 20% by weight or more.

  In the method for producing a polyurethane resin of the present invention, the polyisocyanate used as the isocyanate component may be any conventionally known one, and is not particularly limited. For example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) , Naphthylene diisocyanate, aromatic polyisocyanates such as xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate, and mixtures thereof. . Among these, TDI and its derivatives, or MDI and its derivatives are preferable, and these may be used alone or in combination.

  Examples of TDI and derivatives thereof include a mixture of 2,4-TDI and 2,6-TDI, a terminal isocyanate prepolymer derivative of TDI, and the like. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate, and a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  Among these isocyanates, soft polyurethane resins and semi-rigid polyurethane resin products have TDI and its derivatives and / or MDI and its derivatives, and hard polyurethane resins have a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate. Preferably used.

  The mixing ratio of these polyisocyanates and polyols is not particularly limited, but when expressed in terms of isocyanate index ([isocyanate group] / [active hydrogen group capable of reacting with isocyanate groups]), generally the range is 60 to 400. preferable.

  In the method for producing a polyurethane resin of the present invention, the catalyst used may be a conventionally known catalyst used for producing a polyurethane resin, and is not particularly limited. For example, an organometallic catalyst, a tertiary amine catalyst A quaternary ammonium salt catalyst is preferable.

  The organometallic catalyst may be a conventionally known one, and is not particularly limited. For example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, Examples include dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

  The tertiary amine catalyst may be a conventionally known one, and is not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetra Methylpropylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′ , N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1 , 8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpipe Gin, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethyl And tertiary amine compounds such as aminopropylimidazole.

  The quaternary ammonium salt catalyst may be a conventionally known one, and is not particularly limited. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium water such as tetramethylammonium hydroxide salts, and the like. Examples thereof include tetraalkylammonium organic acid salts such as oxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  In the method for producing a polyurethane resin of the present invention, a foaming agent can be used if necessary. The foaming agent is not particularly limited, and examples thereof include 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3-heptafluoro Fluorocarbon compounds such as propane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low boiling point hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, and acetone, and a mixture is used. be able to. As the low-boiling hydrocarbons, hydrocarbons having a boiling point of usually −30 to 70 ° C. are usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane, and mixtures thereof.

The amount of the foaming agent used is determined according to the desired density and foam physical properties. Specifically, the foam density obtained is usually 5 to 1000 kg / m ³ , preferably 10 to 500 kg / m ^3. Selected as

  In the method for producing a polyurethane resin of the present invention, a surfactant can be used as a foam stabilizer if necessary. Examples of the surfactant to be used include conventionally known organosilicone surfactants, and specifically, nonionic systems such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Surfactant or a mixture thereof is exemplified. Their use amount is usually 0.1 to 10 parts by weight per 100 parts by weight of polyol.

  In the method for producing a polyurethane resin of the present invention, a crosslinking agent or a chain extender can be used if necessary. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, ethylenediamine, and xylylene diene. Examples thereof include polyamines such as amine and methylenebisorthochloroaniline.

  In the method for producing a polyurethane resin of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant used include reactive flame retardants such as phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl Tertiary phosphates such as phosphate, halogen-containing tertiary phosphates such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, halogens such as dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A Examples include organic compounds, inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount is not particularly limited and varies depending on the required flame retardancy, but is usually 4 to 20 parts by weight with respect to 100 parts by weight of the polyol.

  In the method for producing a polyurethane resin of the present invention, if necessary, a colorant, an antioxidant, and other conventionally known additives can be used. The type and amount of these additives may be within the normal usage range of the additive used.

  The method for producing the polyurethane resin of the present invention is carried out, for example, by rapidly mixing and stirring the mixed solution obtained by mixing the raw materials described above, and then injecting the mixture into a suitable container or mold to perform foam molding. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. High-pressure, low-pressure, and spray-type equipment can be used as the polyurethane foaming machine.

  Examples of the polyurethane resin product obtained by the method for producing a polyurethane resin of the present invention include an elastomer that does not use a foaming agent, a polyurethane foam that uses a foaming agent, and the like. It is suitably used for the production of polyurethane foam products.

  Examples of polyurethane foam products include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, etc. The polyurethane resin production method of the present invention is a flexible polyurethane foam car sheet used as an automobile interior material, semi-rigid polyurethane. It is particularly preferably used for the production of insulation panels made of foam instrument panels and handles and rigid polyurethane foam.

In the present invention, the flexible polyurethane foam generally refers to a reversibly deformable foam having an open cell structure and exhibiting high air permeability (Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers ( Germany), p. 161-233, and Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. 150-221). The physical properties of the flexible urethane foam are not particularly limited. Generally, the density is 10 to 100 kg / m ³ , the compressive strength (ILD 25%) is 200 to 8000 kPa, and the elongation is 80 to 500%. It is.

The semi-rigid polyurethane foam is a reversibly deformable foam having an open cell structure and high air permeability like the flexible polyurethane foam, although the foam density and compressive strength are higher than those of the flexible polyurethane foam (Gunter). Oertel, "Polyurethane Handbook" (1985 edition) Hanser Publishers (Germany), p. 223-233, and Keiji Iwata "Polyurethane resin handbook" (first edition in 1987) Nikkan Kogyo Shimbun, p. 211-221) . Moreover, since the polyol and isocyanate raw material to be used are the same as that of the flexible polyurethane foam, it is generally classified as a flexible polyurethane foam. The physical properties of the semi-rigid urethane foam are not particularly limited, but generally, the density is 40 to 800 kg / m ³ , the compressive strength (ILD 25%) is 10 to 200 kPa, and the elongation is 40 to 200%. It is. In the present invention, the flexible polyurethane foam may include a semi-rigid polyurethane foam due to the raw materials used and the foam physical properties.

Further, rigid polyurethane foam refers to a foam having a highly crosslinked closed cell structure and cannot be reversibly deformed (Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany), p. 234. 313, and Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, see pages 224 to 283). The physical properties of the rigid urethane foam are not particularly limited, but are generally in the range of a density of 10 to 100 kg / m ³ and a compressive strength of 50 to 1000 kPa.

  The polyol composition of the present invention has been found to have a low viscosity before dehydration, better handling, good dispersion stability, and excellent storage stability and dispersion stability.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, it is not limited to these.

  In the following examples, the volume average particle size ([MV] value) was measured in a HRA mode and a UPA mode using a microtrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.).

  The viscosity before and after dehydration was measured with a B-type viscometer according to JIS K-1557-5.

  In the storage stability test, the dehydrated polyol composition was placed in a transparent glass bottle and allowed to stand at room temperature for 1 month, and the presence or absence of latex sediment was visually observed.

  In the dispersion stability test, 25 g of the dehydrated vinyl chloride polymer / polyol dispersion was filtered through a 200 mesh (75 μm) SUS wire mesh, washed thoroughly with water, and then dried with a vacuum dryer (70 ° C. × 8 hours). The gel amount (aggregate amount: ppm) was determined. If the gel amount is 300 ppm or less, it can be said that the dispersion stability is excellent.

Example 1
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 1.2 g of 5 wt% sodium lauryl sulfate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, a 5% by weight aqueous sodium lauryl sulfate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization vessel decreased to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 140 g of a 5 wt% aqueous sodium lauryl sulfate solution was added to obtain a latex solution containing vinyl chloride polymer particles. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of sodium lauryl sulfate in the vinyl chloride polymer particles was 2.9 parts by weight (based on 100 parts by weight of the vinyl chloride polymer, the same applies hereinafter).

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 60,000 mPa · s. Since the viscosity was as low as 60,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle size ([MV] value) of the vinyl chloride polymer particles was measured and found to be 4.2 μm. Moreover, it was 3900 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 150 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight and the viscosity was 3900 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Example 2
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 1.2 g of 5 wt% sodium lauryl sulfate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, a 5% by weight aqueous sodium lauryl sulfate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can drops to 0.7 MPa, the unreacted vinyl chloride monomer is recovered, 140 g of a 5% by weight polyoxyethylene alkylsulfosuccinate aqueous solution is added, and the vinyl chloride polymer particle-containing latex is added. A solution was obtained. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of sodium lauryl sulfate and disodium polyoxyethylene alkylsulfosuccinate in the vinyl chloride polymer particles was 2.9 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 60,000 mPa · s. Since the viscosity was as low as 60,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 1.5 μm. Moreover, it was 4300 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 140 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the used polyol composition was 40% by weight, and the viscosity was 4300 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Example 3
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer, 9.6 g of 5 wt% potassium laurate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, 45 g of a 5 wt% aqueous potassium laurate solution and 125 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution were added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 130 g of 5 wt% sodium lauryl sulfate was added to obtain a latex solution containing vinyl chloride polymer particles. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of sodium lauryl sulfate in the vinyl chloride polymer particles was 1.2 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 70,000 mPa · s. Since the viscosity was as low as 70,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispae, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 0.45 μm. Moreover, it was 5000 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 70 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight, and the viscosity was 5000 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Example 4
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer, 9.6 g of 5 wt% potassium laurate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, 45 g of a 5 wt% aqueous potassium laurate solution and 125 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution were added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can is reduced to 0.7 MPa, unreacted vinyl chloride monomer is recovered, and 130 g of 5% by weight polyoxyethylene alkylsulfosuccinate aqueous solution is added, and the latex containing vinyl chloride polymer particles is added. A solution was obtained. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The polyoxyethylene alkylsulfosuccinic acid disodium content in the vinyl chloride polymer particles was 1.2 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 60,000 mPa · s. Since the viscosity was as low as 60,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle size ([MV] value) of the vinyl chloride polymer particles was measured and found to be 1.7 μm. Moreover, it was 4300 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 40 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the used polyol composition was 40% by weight, and the viscosity was 4300 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Example 5
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 5 wt% and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, a 5% by weight aqueous sodium dodecylbenzenesulfonate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization vessel decreased to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 140 g of a 5 wt% aqueous sodium lauryl sulfate solution was added to obtain a latex solution containing vinyl chloride polymer particles. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.56 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of sodium lauryl sulfate in the vinyl chloride polymer particles was 1.3 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 50,000 mPa · s. Since the viscosity was as low as 50,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 0.71 μm. Moreover, it was 4500 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 100 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight, and the viscosity was 4500 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Example 6
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer, 9.6 g of 5 wt% potassium laurate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, a 5% by weight aqueous solution of polyoxyethylene alkylsulfosuccinate disodium was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization vessel decreased to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 140 g of a 5 wt% aqueous sodium lauryl sulfate solution was added to obtain a latex solution containing vinyl chloride polymer particles. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of sodium lauryl sulfate and disodium polyoxyethylene alkylsulfosuccinate in the vinyl chloride polymer particles was 2.9 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 60,000 mPa · s. Since the viscosity was as low as 60,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 1.5 μm. Moreover, it was 4100 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 110 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight and the viscosity was 4100 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Example 7
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 1.2 g of 5 wt% sodium lauryl sulfate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, a 5% by weight aqueous sodium lauryl sulfate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization vessel decreased to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 140 g of a 5 wt% aqueous sodium lauryl sulfate solution was added to obtain a latex solution containing vinyl chloride polymer particles. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of sodium lauryl sulfate in the vinyl chloride polymer particles was 2.9 parts by weight.

  162.4 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin-based polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy and was 20,000 mPa · s as a result of measuring the viscosity before dehydration. Since the viscosity was as low as 20,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 15% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispae, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 0.45 μm. Moreover, it was 2300 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 90 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 15% by weight, and the viscosity was 2300 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Comparative Example 1
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 60 g of a 5 wt% sodium alkyldiphenyl ether sodium disulfonate solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of the polymerization, 170 g of a 5% by weight aqueous sodium alkyldiphenyl ether disulfonate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can drops to 0.7 MPa, the unreacted vinyl chloride monomer is recovered, and 140 g of a 5 wt% sodium alkyldiphenyl ether disulfonate aqueous solution is added to obtain a latex solution containing vinyl chloride polymer particles. It was. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.10 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of the organic compound having a sulfate ester salt and a sulfosuccinate in the vinyl chloride polymer particles was 0 part by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 120,000 mPa · s. Since the viscosity was as high as 120,000 mPa · s, mixing and dispersion were difficult. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 1.0 μm. Moreover, it was 4400 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 1500 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight, and the viscosity was 4400 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Comparative Example 2
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 60 g of a 5 wt% sodium alkylnaphthalenesulfonate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, 170 g of a 5% by weight aqueous sodium alkylnaphthalenesulfonate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can drops to 0.7 MPa, the unreacted vinyl chloride monomer is recovered, 170 g of 5 wt% sodium alkylnaphthalenesulfonate aqueous solution is added, and a latex solution containing vinyl chloride polymer particles is obtained. It was. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.10 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of the organic compound having a sulfate ester salt and a sulfosuccinate in the vinyl chloride polymer particles was 0 part by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 120,000 mPa · s. Since the viscosity was as high as 120,000 mPa · s, mixing and dispersion were difficult. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 1.0 μm. Moreover, it was 4400 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 1400 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight, and the viscosity was 4400 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Comparative Example 3
In a 2.5 L polymerization vessel, 800 g of deionized water, 600 g of vinyl chloride monomer, 1.2 g of 5 wt% sodium lauryl sulfate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, 170 g of a 5% by weight aqueous sodium alkylnaphthalenesulfonate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can drops to 0.7 MPa, the unreacted vinyl chloride monomer is recovered, and 2.4 g of 5 wt% sodium lauryl sulfate solution is added to obtain a latex solution containing vinyl chloride polymer particles. It was. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of the organic compound having a sulfate ester salt and a sulfosuccinate in the vinyl chloride polymer particles was 0.03 part by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 60,000 mPa · s. Since the viscosity was as low as 60,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispae, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 0.45 μm. Moreover, it was 5100 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 1100 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of vinyl chloride polymer particles in the polyol composition used was 40% by weight and the viscosity was 5100 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Comparative Example 4
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer, 9.6 g of 5 wt% sodium lauryl sulfate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, 170 g of a 5% by weight aqueous sodium lauryl sulfate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can drops to 0.7 MPa, the unreacted vinyl chloride monomer is recovered, and 325 g of a 15% by weight aqueous sodium alkylnaphthalenesulfonate solution is added to obtain a latex solution containing vinyl chloride polymer particles. It was. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of the organic compound having a sulfate ester salt and a sulfosuccinate in the vinyl chloride polymer particles was 10.6 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 60,000 mPa · s. Since the viscosity was as low as 60,000 mPa · s, it could be easily mixed and dispersed. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispae, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 0.45 μm. Moreover, it was 5200 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 1000 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of the vinyl chloride polymer particles in the polyol composition used was 40% by weight and the viscosity was 5200 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

Comparative Example 5
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer, 59.4 g of 5 wt% sodium lauryl sulfate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 66 ° C. to initiate polymerization. From 60 minutes after the start of polymerization, 170 g of a 5% by weight aqueous sodium lauryl sulfate solution was added at a rate of 35 ml per hour, and the addition was stopped after 350 minutes. When the pressure in the polymerization can decreased to 0.7 MPa, unreacted vinyl chloride monomer was recovered to obtain a latex solution containing vinyl chloride polymer particles. As a result of measuring the particle size of the vinyl chloride polymer particles in the obtained latex solution, the volume average particle size ([MV] value) is 0.08 μm, and the concentration of the vinyl chloride polymer particles is 32.6% by weight. The content of the organic compound having a sulfate ester salt and a sulfosuccinate in the vinyl chloride polymer particles was 2.1 parts by weight.

  613.5 g of the obtained latex solution and 300 g of a commercially available polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin polyether polyol, OH number: 32.9 KOH / g] Disperser [(trade name) T. K. Homodispa, manufactured by Primix Co., Ltd.]. The mixture was creamy, and as a result of measuring the viscosity before dehydration, it was 200,000 mPa · s. Since the viscosity was as high as 200,000 mPa · s, it was difficult to disperse. The obtained mixture was put into a 2 L eggplant-shaped flask and dehydrated using a rotary evaporator. As the dehydration progressed, the mixture became fluid and became a viscous fluid at the end of the dehydration, and a polyol composition having a vinyl chloride polymer particle concentration (content) of 40% by weight was obtained.

  The polyol composition after completion of the dehydration was converted to T.P. K. After stirring uniformly with a homodispers, the volume average particle diameter ([MV] value) of the vinyl chloride polymer particles was measured and found to be 0.15 μm. Moreover, it was 8100 mPa * s as a result of measuring a viscosity. As a result of a storage stability test for one month, no sedimentation of particles was observed, and the sample was in a uniform state. Furthermore, as a result of conducting a dispersion stability test, the gel amount was 1300 ppm.

  Next, when a flexible polyurethane foam was prepared using the obtained polyol composition, the content of the vinyl chloride polymer particles in the used polyol composition was 40% by weight, and the viscosity was 8100 mPa · s. The handling performance was good.

  The flexible polyurethane foam was prepared by preparing 83.34 g of a vinyl chloride polymer particle-containing polyol composition, 83.34 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company, a polymer polyol. , OH value: 34.6 KOH / g] 3.42 g, foam stabilizer [(trade name) TEGOSTAB B4113LF, manufactured by Goldschmidt] 1.8 g, diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g, water 1. 8 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine] 1.44 g were mixed, and then commercially available isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MDI isocyanate. DOO, the NCO% = 31.7%) was added as the isocyanate index is 98, the mixture was stirred for 5 seconds at 6500 rpm, poured into a mold, the reaction was carried out to obtain a flexible polyurethane foam.

  The polyol composition of the present invention is suitable for the polyurethane resin manufacturing industry because it can produce a polyurethane resin with less sediment, excellent storage stability and dispersion stability, good handling performance, and good dispersion stability. Have the potential to be used.

Claims (5)

A vinyl chloride polymer particle having a volume average particle diameter ([MV] value) of 0.2 to 5 μm is contained in a polyol in an amount of 10 to 50% by weight, and the vinyl chloride polymer particle contains 100% by weight of the vinyl chloride polymer. A polyol composition comprising 0.05 to 10 parts by weight of at least one selected from organic compounds having a sulfate ester salt and a sulfosuccinate with respect to parts. 2. The polyol composition according to claim 1, wherein the viscosity is 10,000 mPa · s or less. 3. A latex solution containing vinyl chloride polymer particles having a volume average particle size ([MV] value) of 0.1 to 2 [mu] m is mixed with a polyol, and the resulting mixture is dehydrated. The manufacturing method of the polyol composition as described in above. A method for producing a polyurethane resin, comprising reacting the polyol composition according to claim 1 or 2 with a polyisocyanate component in the presence of a catalyst. The method for producing a polyurethane resin according to claim 4, wherein the reaction is carried out in the presence of a blowing agent in addition to the catalyst.