JP2016098356A - Vinyl chloride polymer latex, polyol composition and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition excellent in dispersion stability and sedimentation stability, a vinyl chloride polymer latex for manufacturing the polyol composition and a manufacturing method of a polyol composition using the vinyl chloride polymer latex.SOLUTION: There are provided a vinyl chloride polymer latex containing 100 pts.wt. of a vinyl chloride polymer having volume average particle diameter ([MV] value) of 0.2 to 1.6 μm and 0.5 to 10 pts.wt. of an alkali salt of a resin acid or the alkali salt of a copolymer of α-olefin having neutralization degree of 0.6 to 0.9 and maleic acid anhydride, a polyol composition containing 5 to 40 wt.% of the vinyl chloride polymer having volume average particle diameter ([MV] value) of 0.2 to 1.6 μm and 0.5 to 10 pts.wt. of the alkali salt of the resin acid or the alkali salt of the copolymer of α-olefin having neutralization degree of 0.6 to 0.9 and maleic acid anhydride as a dispersant based on 100 pts.wt. of the vinyl chloride polymer and a manufacturing method of the polyol composition.SELECTED DRAWING: None

Description

  The present invention relates to a vinyl chloride polymer latex, a polyol composition and a method for producing the same. 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 of polyvinyl chloride particles are dispersed, but generation of coarse particles that are aggregates of polyvinyl chloride particles in the dehydrated polyol composition. In addition, dispersion stability and sedimentation stability were insufficient, such as precipitation of polyvinyl chloride in the polyol composition after dehydration. Patent Document 2 discloses a method for preparing a polyol in which a polyvinyl chloride monomer is polymerized in a polyol to disperse polyvinyl chloride particles. However, dispersion stability such as aggregation of the polyol composition and generation of coarse particles is disclosed. Was insufficient.

  In addition, the applicant of the present invention previously dispersed vinyl chloride polymer particles and / or vinyl chloride-unsaturated vinyl copolymer particles having a volume average particle diameter ([MV] value) of 0.05 μm or more and 1 μm or less in a polyol. Discloses a polyol composition containing 10 wt% or more and 50 wt% or less (Patent Document 3). In the polyol composition after dehydration, generation of coarse particles due to aggregation of polyvinyl chloride particles and polyvinyl chloride particles Dispersion stability and sedimentation stability were insufficient.

JP-A-1-65160 Japanese Patent Laid-Open No. 3-97715 JP 2010-31169 A

  The present invention has been made in view of the above background art, and an object thereof is to provide a polyol composition excellent in dispersion stability and sedimentation stability, and a vinyl chloride polymer latex for producing the polyol composition. .

  As a result of intensive studies to solve the above problems, the present inventors have found that as a dispersant, 100 parts by weight of a vinyl chloride polymer having a volume average particle diameter ([MV] value) of 0.2 to 1.6 μm. A vinyl chloride polymer comprising 0.5 to 10 parts by weight of an alkali salt of a resin acid or an alkali salt of a copolymer of an α-olefin and maleic anhydride having a neutralization degree of 0.6 to 0.9 It was found that the dispersion stability and sedimentation stability of the vinyl chloride polymer particles in the polyol composition were improved by mixing and dehydrating the latex and the polyol, and the present invention was completed. That is, in the present invention, 100 parts by weight of a vinyl chloride polymer having a volume average particle size ([MV] value) of 0.2 to 1.6 μm is used as a dispersant as an alkali salt of resin acid or a degree of neutralization of 0. A vinyl chloride polymer latex containing 0.5 to 10 parts by weight of an alkali salt of a copolymer of .alpha.-olefin and maleic anhydride of 6 to 0.9, volume average particle diameter ([MV] value) ) Is contained in an amount of 0.2 to 1.6 μm of vinyl chloride polymer, and 100 parts by weight of the vinyl chloride polymer is used as a dispersant as an alkali salt of resin acid or a degree of neutralization of 0. A polyol composition containing 0.5 to 10 parts by weight of an alkali salt of a copolymer of 6 to 0.9 α-olefin and maleic anhydride, and a method for producing the polyol composition .

  Hereinafter, the present invention will be described in detail below.

  The vinyl chloride polymer latex of the present invention contains 0.5 to 10 parts by weight of a dispersant with respect to 100 parts by weight of a vinyl chloride polymer having a volume average particle diameter ([MV] value) of 0.2 to 1.6 μm. It is a waste. The dispersion stability of the polyol composition containing 5 to 40% by weight of this vinyl chloride polymer latex is improved, and the number of coarse particles, which are aggregates of vinyl chloride polymer particles, is reduced and improved. This polyol composition can be produced by mixing the vinyl chloride polymer latex in a polyol and dehydrating it.

  When the content of the dispersant in the vinyl chloride polymer latex is less than 0.5 parts by weight or more than 10 parts by weight, the polyvinyl chloride polymer particles in the polyol composition after dehydration are aggregated to form aggregates. Coarse particles are generated, and the dispersion stability and sedimentation stability are poor. Furthermore, in order to further improve the dispersion stability and sedimentation stability, the content of the dispersant is preferably 1 to 6 parts by weight.

  The dispersant used in the present invention is an alkali salt of a resin acid or an alkali salt of a copolymer of an α-olefin and maleic anhydride. By these, aggregation of the vinyl chloride polymer particles in the polyol composition after dehydration is prevented, and dispersion stability and sedimentation stability are improved.

  Since the resin acid alkali salt used in the present invention has a high dispersion effect and is inexpensive, a rosin compound is preferred. The rosin compound is not particularly defined, and examples thereof include abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, d-pimalic acid, iso-d-pimalic acid, and levopimaric acid. These resin acids are representative components contained in rosin, and those commercially available such as gum rosin, tall rosin, and wood rosin can be used as the dispersant of the present invention. Further, modified rosins such as disproportionated rosin mainly composed of dehydroabietic acid or dihydroabietic acid, disproportionated reaction, hydrogenated rosin mainly composed of dihydroabietic acid, and polymerized rosin mainly composed of abietic acid dimer are also available. Can be used without problems. These resin acids are alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, aluminum salts, salts such as iron, zinc, other heavy metal salts and ammonium salts. The salt may be used alone or in combination of two or more. The alkali salt of the resin acid may be used as it is, a partially neutralized product, or a completely neutralized product.

  The α-olefin used in the alkali salt of the copolymer of α-olefin and maleic anhydride used in the present invention is a linear or branched olefin having a carbon-carbon double bond unsaturated double bond at the α-position. The olefin having 2 to 12 carbon atoms is preferable, and the olefin having 2 to 8 carbon atoms is particularly preferable. Typical α-olefins include ethylene, propylene, n-butylene, isobutylene, n-pentene and 2-methyl-1-butene. , 3-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, etc. Isobutylene is preferred, and these olefins may be used alone or in combination of two or more. The alkali salt of the copolymer of α-olefin and maleic anhydride used in the present invention is, for example, a copolymer of n-butylene and maleic anhydride, a copolymer of isobutylene and maleic anhydride, ethylene, propylene and anhydrous. Examples thereof include a maleic acid copolymer.

  The alkali salt of the copolymer of α-olefin and maleic anhydride used in the present invention is a partially neutralized product. As a method for obtaining a partially neutralized product, when isobutylene and maleic anhydride copolymer are dissolved, the amount of alkali added is calculated stoichiometrically. That is, when the maleic anhydride of the copolymer is completely neutralized to make maleic acid, the neutralization degree is 1.0 and the alkali addition amount for partial neutralization is obtained. The neutralization degree of the alkali salt of the copolymer of α-olefin and maleic anhydride used in the dispersant of the present invention is 0.6 to 0.9. If the degree of neutralization is less than 0.6 or exceeds 0.9, the polyvinyl chloride polymer particles in the polyol composition after dehydration aggregate to produce coarse particles that are aggregates, and dispersion stability and sedimentation Stability is inferior. Furthermore, in order to further improve the dispersion stability and sedimentation stability, the neutralization degree is preferably 0.7 to 0.9.

  The vinyl chloride polymer contained in the vinyl chloride polymer latex of the present invention has a volume average particle diameter ([MV] value) of 0.2 to 1.6 μm. The reason is that the dispersion stability of the polyol composition containing the vinyl chloride polymer obtained by mixing and dehydrating the vinyl chloride polymer latex in the polyol is improved, and the coarse particles which are aggregates of the vinyl chloride polymer particles are reduced. It is because it becomes favorable. When it is less than 0.2 μm, the dispersion stability and sedimentation stability of the vinyl chloride polymer in the polyol composition are poor. When it exceeds 1.6 μm, the dispersion stability of the vinyl chloride polymer in the polyol composition is excellent, but the sedimentation stability is poor. In order to further improve the dispersion stability and sedimentation stability, the volume average particle diameter ([MV] value) of the vinyl chloride polymer contained in the vinyl chloride polymer latex is preferably 0.2 to 0.6 μm.

  In the present invention, the volume average particle diameter ([MV] value) of the vinyl chloride polymer may be any apparatus as long as it is a particle size distribution measuring apparatus based on the generally known laser diffraction method and dynamic light scattering method. Even if it is used, it can be measured and there is no particular limitation. For example, it can be measured with a laser diffraction / scattering particle size measuring device (trade name: LA-920, manufactured by Horiba, Ltd.).

  The concentration of the vinyl chloride polymer contained in the vinyl chloride polymer latex of the present invention is not particularly limited, but is preferably 5 to 40% by weight, more preferably 10 to 30% by weight in order to further improve the dispersion stability. preferable.

  The vinyl chloride polymer latex of the present invention contains an emulsifier in addition to an alkali salt of a resin acid or an alkali salt of an α-olefin and maleic anhydride copolymer having a neutralization degree of 0.6 to 0.9 as a dispersant. You may contain. Examples of the emulsifier include alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate, higher fatty acid salt, sulfate ester salt, sulfosuccinate and the like. Examples of the alkyl benzene sulfonate include sodium dodecyl benzene sulfonate and ammonium dodecyl benzene sulfonate, and examples of the alkyl naphthalene sulfonate include sodium alkyl naphthalene sulfonate and potassium alkyl naphthalene sulfonate. Examples of the alkyl diphenyl ether disulfonate include sodium alkyl diphenyl ether disulfonate and potassium alkyl diphenyl ether disulfonate. Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali. Examples of sulfate salts include alkyl sulfate salts such as sodium lauryl sulfate and sodium myristyl sulfate, polyoxyethylene alkylaryl sulfate salts, and the like. Examples of the sulfosuccinate include disodium polyoxyethylene alkyl sulfosuccinate, disodium polyoxyethylene alkyl ether sulfosuccinate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene lauryl ether sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dioctyl sulfosuccinate. And sodium dihexyl sulfosuccinate.

  The vinyl chloride polymer latex of the present invention can be prepared by polymerizing a vinyl chloride monomer alone. There is no restriction | limiting in particular as a polymerization method except using a specific amount of dispersing agent, On the conditions that the volume average particle diameter ([MV] value) of the produced | generated vinyl chloride polymer will be 0.2-1.6 micrometers. Any method generally known as a method for producing a vinyl chloride polymer latex 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 the dispersant used is 0.5 to 10 parts by weight and preferably 3 to 6 parts by weight with respect to 100 parts by weight of the vinyl chloride monomer. When the amount used is less than 0.5 parts by weight, the dispersion stability and sedimentation stability cannot be improved, and when it exceeds 10 parts by weight, the dispersion stability and sedimentation stability cannot be improved.

  The polyol composition of the present invention is obtained by dispersing a vinyl chloride polymer in a polyol, and the volume average particle diameter ([MV] value) of the vinyl chloride polymer contained in the polyol is 0.2 to 1.6 μm. The content is 5 to 40% by weight based on the polyol composition. When the volume average particle diameter ([MV] value) of the vinyl chloride polymer is less than 0.2 μm, the dispersion stability and the sedimentation stability are inferior, and when it exceeds 1.6 μm, the sedimentation stability is inferior. If the content (concentration) of the vinyl chloride polymer is less than 5% by weight, there is a fear that the improvement of the hardness of the polyurethane foam expected as an effect of adding the polyol may be insufficient. There is a risk of becoming stiff. In order to further improve the hardness of the polyurethane foam expected as an additive effect of the polyol, 5 to 35% by weight is preferable.

  In the present invention, in order to confirm that the vinyl chloride polymer contained in the polyol is present, the polyol containing the vinyl chloride polymer may be simply diluted with water and the particle size distribution may be measured, or the organic solvent You may measure using. Examples of the organic solvent include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, Ethyl cellosolve, acetone, ethyl acetate, diacetone alcohol and the like can be used.

  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 Chemical Industries), Exenol (trade name: manufactured by Asahi Glass), Actol (trade name: manufactured by Mitsui Chemicals Polyurethane), VORANOL, which are currently commercially available. (Trade name: manufactured by DOW).

  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.

  The polyol composition of the present invention contains 0.5 to 10 parts by weight of a dispersant with respect to 100 parts by weight of a vinyl chloride polymer having a volume average particle size ([MV] value) of 0.2 to 1.6 μm. Is. Thereby, dispersion stability and sedimentation stability are improved. When the content of the dispersant is less than 0.5 parts by weight, the amount of coarse particles increases, and the dispersion stability and sedimentation stability cannot be improved. When the content exceeds 10 parts by weight, the dispersion stability and sedimentation stability are also increased. The problem that is inferior occurs. In order to further improve the dispersion stability and sedimentation stability, 3 to 6 parts by weight is preferable.

  The polyol composition of the present invention may contain a catalyst, a foaming agent, a surfactant, a cross-linking agent, a chain extender, a flame retardant, a colorant, an antiaging agent, and other conventionally known additives as necessary. You may contain.

  The method for producing a polyol composition of the present invention comprises, for example, mixing a vinyl chloride polymer latex of the present invention containing a vinyl chloride polymer having a volume average particle size ([MV] value) of 0.2 to 1.6 μm and a polyol, The obtained mixture is characterized by dehydration.

  In the present invention, by mixing a vinyl chloride polymer latex containing a vinyl chloride polymer having a volume average particle size ([MV] value) of 0.2 to 1.6 μm and a polyol, water, a polyol, and a vinyl chloride polymer 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 Homo dispa (trade name: manufactured by PRIMIX) If the homogenization is insufficient, coarse particles due to aggregation of the vinyl chloride polymer may occur in the subsequent dehydration step.

  In the method for producing a polyol composition of the present invention, for example, when mixing a vinyl chloride polymer latex containing a vinyl chloride polymer having a volume average particle diameter ([MV] value) of 0.2 to 1.6 μm and a polyol, If necessary, a catalyst, a foaming agent, a surfactant, a crosslinking agent, a chain extender, a flame retardant, a colorant, an antiaging agent, and other conventionally known additives described below may be mixed.

  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 60 ° 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 or dehydration by a vacuum dryer can be exemplified at a laboratory level. Moreover, the method etc. which use a planetary mixer as a stirrer corresponding to high-viscosity stirring and an evaporation pot which can be decompressed are exemplified.

  In order to prevent the vinyl chloride polymer 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.

  A method for producing a polyurethane resin 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. Its features.

  In the method for producing a polyurethane resin, 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, polyester polyols, and polymers are within the scope of the present invention. Polyols such as 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, in order to further improve the hardness of the polyurethane foam expected as an effect of adding a polyol, the vinyl chloride polymer relative to the polyol used (including the polyol in the polyol composition of the present invention) is used. The content is preferably 10% by weight or more, and more preferably 20% by weight or more.

  In the method for producing a polyurethane resin, the polyisocyanate used as the isocyanate component may be any conventionally known one, and is not particularly limited. Examples thereof include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthylene diene. Examples thereof include aromatic polyisocyanates such as isocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate and 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, 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 fourth catalyst A class ammonium salt catalyst etc. are mentioned as a suitable thing.

  The organometallic catalyst may be a conventionally known one, and is not particularly limited. 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, 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 polyurethane resin production method, if necessary, a surfactant can be used as a foam stabilizer. 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, if necessary, a crosslinking agent or a chain extender can be used. 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, 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, if necessary, a colorant, an anti-aging agent, 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 polyurethane resin is produced by, for example, rapidly mixing and stirring the above-mentioned mixed liquid containing raw materials, and then injecting the mixture into a suitable container or mold for 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 polyurethane resin products obtained by the polyurethane resin production method include elastomers that do not use a foaming agent, polyurethane foams that use a foaming agent, and the like, and the polyurethane resin production method is used to produce such polyurethane foam products. Preferably used.

  Examples of polyurethane foam products include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, etc., but the polyurethane resin is produced by a flexible polyurethane foam car sheet used as an automobile interior material, and semi-rigid polyurethane foam in-line. It is particularly suitably used for the manufacture of heat insulating materials made of instrument panels, handles, and rigid polyurethane foam.

Here, 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, see pages 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. A flexible polyurethane foam may contain a semi-rigid polyurethane foam from the raw material to be used and 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.

  It has been found that the polyol composition of the present invention is excellent in dispersion stability and sedimentation stability, and that the polyol composition of the present invention can be produced by using the vinyl chloride polymer latex of the present invention. It was.

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

<Measurement of Volume Average Particle Diameter ([MV] Value) of Vinyl Chloride Polymer Latex>
A measurement sample prepared by adding water to a vinyl chloride polymer latex so that the laser transmittance is 84 to 86% and adjusting the concentration was measured using a laser diffraction / scattering particle size measuring device (trade name: LA-920, Horiba). The volume average particle diameter ([MV] value) of the vinyl chloride polymer latex was measured using a manufacturing method.

<Dispersion stability test of polyol composition after dehydration>
The dispersion stability test of the polyol composition after dehydration was conducted according to JIS-K-5400 and “PVC paste processing—features and application” (1998) Rubber Digest p. The crush test described in No. 139 was performed, and the polyol composition after dehydration was placed in the deepest part of the inclined grind gauge groove having a groove of 300 μm. When the coarse particle diameter is small, the dispersion stability is improved when the coarse particle diameter is the depth at which the coarse particles appearing on the surface of the polyol composition first appear and the depth at which the fifth coarse particle appears. It was excellent.

<Sedimentation stability test of polyol composition after dehydration>
In the sedimentation stability test, the dehydrated polyol composition was placed in a centrifugal sedimentation tube, centrifuged at 4000 rpm for 1 hour, and the thickness of the supernatant transparent layer of the upper portion of the polyol composition produced by centrifugation was measured. The ratio with respect to the total length of the polyol composition put in was determined, and the sedimentation stability was excellent when the thickness of the transparent layer was small.

Production Example 1
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% by weight aqueous potassium laurate solution and 125 g of a 5% by weight 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, the unreacted vinyl chloride monomer is recovered, the volume average particle size ([MV] value) is 0.26 μm, and the concentration of the vinyl chloride polymer is 36% by weight. A vinyl chloride polymer latex of a vinyl chloride polymer was obtained.

Production Example 2
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer 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% by weight aqueous potassium laurate solution and 125 g of a 5% by weight 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 vessel decreased to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 118 g of 5 wt% aqueous potassium laurate solution and 12 g of 5 wt% aqueous sodium dodecylbenzenesulfonate were added. A vinyl chloride polymer latex having an average particle size ([MV] value) of 0.6 μm and a vinyl chloride polymer concentration of 34% by weight was obtained.

Production Example 3
A 1 m ³ autoclave was charged with 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide and 30 kg of a 15 wt% aqueous sodium dodecylbenzenesulfonate solution, and this polymerization solution was circulated for 3 hours using a homogenizer. After the treatment, the temperature was raised to 45 ° C. to proceed the polymerization. After the pressure has dropped, the polymerization is stopped, the unreacted vinyl chloride monomer is recovered, the solid content 35% by weight particles have an average particle size of 0.55 μm, and the polymer has an excess of 2% by weight. A seed latex 1 containing lauroyl oxide was obtained.

Next, 500 g of deionized water, 500 g of vinyl chloride monomer, 16 g of 5 wt% sodium lauryl sulfate aqueous solution, 95 g of seed latex 1 and 4 g of 0.1 wt% aqueous copper sulfate solution were charged into a 2.5 L autoclave. While raising the temperature to 48 ° C., 150 g of 0.05 wt% aqueous ascorbic acid solution was continuously added throughout the entire polymerization time. Further, 16 g of a 5 wt% aqueous sodium lauryl sulfate solution was continuously added until the polymerization conversion rate was 85% after the start of polymerization. When the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride at 48 ° C. by 2 kg / cm ² , the polymerization was stopped, the unreacted vinyl chloride monomer was recovered, the volume average particle size ([MV] value) was 1.52 μm, A vinyl chloride polymer latex having a vinyl polymer concentration of 38% by weight was obtained.

Production Example 4
As initial charge in a 2.5 L autoclave, 900.0 g of deionized water, 750.0 g of vinyl chloride monomer, 5.0 g of 3 wt% potassium persulfate aqueous solution and 5 wt% sodium dodecylbenzenesulfonate aqueous solution 75 The emulsion polymerization was started by charging 0.0 g and raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, and then the unreacted vinyl chloride monomer was recovered. To this, 235.0 g of a 5% by weight aqueous sodium dodecylbenzenesulfonate solution was added to obtain a vinyl chloride polymer latex having a volume average particle size ([MV] value) of 0.10 μm and a vinyl chloride polymer concentration of 37% by weight. It was.

Production Example 5
Vinyl chloride with a volume average particle size ([MV] value) of 1.62 μm and a vinyl chloride polymer concentration of 41% by weight, in the same manner as in Production Example 3, except that 600 g of vinyl chloride monomer and 80 g of seed latex 1 were used. A polymer latex was obtained.

Production Example 6
After dissolving 30.6 g of sodium hydroxide in 335 g of water at room temperature in a 1 L beaker, 100 g of maleic anhydride copolymer (trade name: Isoban 600, manufactured by Kuraray Co., Ltd.) was placed in this aqueous sodium hydroxide solution and homogenizer at 6000 rpm for 5 minutes. After dispersion, transfer to a 1 L three-necked flask equipped with a condenser, raise the temperature to 94 ° C., conduct a neutralization reaction for 5 hours, filter with a 200 mesh filter cloth, and then neutralize 0.6 isobutylene and anhydrous maleic A 28% by weight aqueous solution of the sodium salt of the acid copolymer was obtained.

Production Example 7
A 28% by weight aqueous solution of isobutylene having a neutralization degree of 0.8 and a sodium salt of maleic anhydride copolymer was obtained in the same manner as in Production Example 6 except that 40.8 g of sodium hydroxide and 360 g of water were used.

Production Example 8
A 28% by weight aqueous solution of isobutylene having a neutralization degree of 0.5 and a sodium salt of maleic anhydride copolymer was obtained in the same manner as in Production Example 6, except that 25.5 g of sodium hydroxide and 325 g of water were used.

Production Example 9
A 28% by weight aqueous solution of isobutylene having a neutralization degree of 1.0 and a sodium salt of maleic anhydride copolymer was obtained in the same manner as in Production Example 6 except that 51 g of sodium hydroxide and 390 g of water were used.

Example 1
Transfer the entire amount of the vinyl chloride polymer latex obtained in Production Example 1 to a 5 liter glass container equipped with a stirrer and disproportionate potassium rosinate (trade name: Longis EK, manufactured by Arakawa Chemical Industries, the same as below) 87 g of a 25% by weight aqueous solution was added to obtain a vinyl chloride polymer latex. The vinyl chloride polymer in the obtained vinyl chloride polymer latex has a volume average particle diameter ([MV] value) of 0.26 μm, a concentration of vinyl chloride polymer of 36% by weight, and a content of disproportionated potassium rosinate of 4 0.0 parts by weight (based on 100 parts by weight of vinyl chloride polymer, the same applies hereinafter).

  Next, 208 g of vinyl chloride polymer latex containing disproportionated rosin and 300 g of a commercially available polyol (trade name: Sannix FA-703, manufactured by Sanyo Chemical Industries, glycerin-based polyether polyol, OH value: 32.9 KOH / g) It was put into a Lee mixer (manufactured by Sanei Seisakusho), mixed and dehydrated. Dehydration was performed using a vacuum pump at −0.08 MPa to obtain a polyol composition having a vinyl chloride polymer content of 20% by weight.

  Table 1 shows the results of the dispersion stability of the obtained dehydrated polyol composition and the sedimentation stability after centrifugation. As shown in Table 1, the sedimentation stability and dispersion stability of the polyol composition were excellent.

実施例２
実施例１と同じ操作で、製造例１より得られた塩化ビニルポリマーラテックスに対し、トールロジン酸カリウム（商品名：バンディスＴ−２５Ｋ、ハリマ化成製）の２５重量％水溶液８７ｇを追加添加し、塩化ビニルポリマーラテックスを得た。得られた塩化ビニルポリマーラテックス中の塩化ビニルポリマーの体積平均粒子径（［ＭＶ］値）は０．２６μｍ、塩化ビニルポリマーの濃度は３６重量％、トールロジン酸カリウムの含有量は４．０重量部だった。

Example 2
In the same operation as in Example 1, 87 g of a 25 wt% aqueous solution of potassium tolrosinate (trade name: Bandis T-25K, manufactured by Harima Chemicals) was added to the vinyl chloride polymer latex obtained in Production Example 1, and chlorinated. A vinyl polymer latex was obtained. The volume average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the content of potassium tollozinate is 4.0 parts by weight. was.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 1 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 1, the sedimentation stability and dispersion stability of the polyol composition were excellent.

Example 3
In the same operation as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the reaction of sodium salt aqueous solution of isobutylene having a neutralization degree of 0.6 obtained in Production Example 6 and a maleic anhydride copolymer. An additional 78 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The product average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 1 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 1, the sedimentation stability and dispersion stability of the polyol composition were excellent.

Example 4
28 weight of sodium salt aqueous solution of isobutylene maleic anhydride copolymer having a neutralization degree of 0.8 obtained in Production Example 7 with respect to the vinyl chloride polymer latex obtained in Production Example 1 in the same operation as in Example 1. A 78% aqueous solution was added to obtain a vinyl chloride polymer latex. The product average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm in volume average particle size ([MV] value), and the concentration of the vinyl chloride polymer is 36% by weight. The content of sodium salt of isobutylene and maleic anhydride copolymer was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 1 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 1, the sedimentation stability and dispersion stability of the polyol composition were excellent.

Example 5
In the same manner as in Example 1, 16 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was added to the vinyl chloride polymer latex obtained in Production Example 1 to obtain a vinyl chloride polymer latex. The volume average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the content of the disproportionated potassium rosinate is 0.00. It was 7 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 1 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 1, the sedimentation stability and dispersion stability of the polyol composition were excellent.

Example 6
In the same manner as in Example 1, 173 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was additionally added to the vinyl chloride polymer latex obtained in Production Example 1 to obtain a vinyl chloride polymer latex. As a result of measuring the particle size of the vinyl chloride polymer in the obtained vinyl chloride polymer latex, the volume average particle size ([MV] value) is 0.26 μm, the concentration of the vinyl chloride polymer is 35% by weight, The content of leveled potassium rosinate was 8 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that 214 g of the vinyl chloride polymer latex was changed. Table 1 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 1, the sedimentation stability and dispersion stability of the polyol composition were excellent.

Example 7
In the same manner as in Example 1, 87 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was added to the vinyl chloride polymer latex obtained in Production Example 2 to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.6 μm, the concentration of the vinyl chloride polymer is 33% by weight, and the content of disproportionated potassium rosinate is 4. It was 0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that the vinyl chloride polymer latex was changed to 227 g. Table 2 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 2, the settling stability and dispersion stability of the polyol composition were excellent.

実施例８
実施例１と同じ操作で、製造例３より得られた塩化ビニルポリマーラテックスに対し、不均化ロジン酸カリウムの２５重量％水溶液８７ｇを追加添加し、塩化ビニルポリマーラテックスを得た。得られた塩化ビニルポリマーラテックス中の塩化ビニルポリマーの体積平均粒子径（［ＭＶ］値）は１．５２μｍ、塩化ビニルポリマーの濃度は３８重量％で、不均化ロジン酸カリウムの含有量は４．０重量部だった。

Example 8
In the same manner as in Example 1, 87 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was additionally added to the vinyl chloride polymer latex obtained in Production Example 3 to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 1.52 μm, the concentration of the vinyl chloride polymer is 38% by weight, and the content of disproportionated potassium rosinate is 4 0.0 part by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that the vinyl chloride polymer latex was changed to 197 g. Table 2 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 2, the settling stability and dispersion stability of the polyol composition were excellent.

Example 9
In the same operation as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the aqueous solution of sodium salt of isobutylene having a neutralization degree of 0.8 obtained in Production Example 7 and a maleic anhydride copolymer. An additional 13.5 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content of was 0.7 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 2 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 2, the settling stability and dispersion stability of the polyol composition were excellent.

Example 10
In the same operation as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the aqueous solution of sodium salt of isobutylene having a neutralization degree of 0.8 obtained in Production Example 7 and a maleic anhydride copolymer. An additional 155 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of vinyl chloride polymer is 35% by weight, and the content of sodium salt of isobutylene maleic anhydride copolymer is 8%. It was a department.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that 214 g of the vinyl chloride polymer latex was changed. Table 2 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 2, the settling stability and dispersion stability of the polyol composition were excellent.

Example 11
In the same manner as in Example 1, the vinyl chloride polymer latex obtained in Production Example 2 was subjected to the aqueous solution of sodium salt solution of isobutylene having a neutralization degree of 0.8 obtained in Production Example 7 and a maleic anhydride copolymer. An additional 77 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.6 μm, the concentration of the vinyl chloride polymer is 34% by weight, and the isobutylene and maleic anhydride copolymer The content of sodium salt was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that the vinyl chloride polymer latex was changed to 228 g. Table 2 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 2, the settling stability and dispersion stability of the polyol composition were excellent.

Example 12
In the same manner as in Example 1, the vinyl chloride polymer latex obtained in Production Example 3 was compared with the sodium chloride of isobutylene and maleic anhydride copolymer obtained in Production Example 7 and having a neutralization degree of 0.8. An additional 65 g of 28% by weight aqueous salt solution was added to obtain a vinyl chloride polymer latex. As a result of measuring the particle size of the vinyl chloride polymer in the obtained vinyl chloride polymer latex, the volume average particle size ([MV] value) is 1.52 μm, the concentration of the vinyl chloride polymer is 38% by weight, and isobutylene And the content of sodium salt of maleic anhydride copolymer was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that the vinyl chloride polymer latex was changed to 197 g. Table 2 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 2, the settling stability and dispersion stability of the polyol composition were excellent.

Comparative Example 1
In the same operation as in Example 1, 208 g of the vinyl chloride polymer latex obtained from Production Example 1 and 300 g of polyol were put into a planetary mixer, and the same operation as in Example 1 was performed. The vinyl chloride polymer content was 20% by weight. A polyol composition was obtained.

  Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability and sedimentation stability of the polyol composition were inferior.

比較例２
製造例２より得られた塩化ビニルポリマーラテックスを用い、塩化ビニルポリマーラテックスを２２１ｇとした以外は、実施例１と同じ操作を行い、塩化ビニルポリマーの含有量が２０重量％のポリオール組成物を得た。

Comparative Example 2
The same procedure as in Example 1 was performed except that the vinyl chloride polymer latex obtained from Production Example 2 was used and the vinyl chloride polymer latex was changed to 221 g to obtain a polyol composition having a vinyl chloride polymer content of 20% by weight. It was.

  Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 3
The same procedure as in Example 1 was performed except that the vinyl chloride polymer latex obtained from Production Example 3 was used and 197 g of the vinyl chloride polymer latex was used to obtain a polyol composition having a vinyl chloride polymer content of 20% by weight. It was.

  Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability of the polyol composition was good, but the sedimentation stability was poor.

Comparative Example 4
The same operation as in Example 1 was performed except that 183 g of the vinyl chloride polymer latex obtained in Production Example 5 was used, and a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained. It was.

  Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability of the polyol composition was good, but the sedimentation stability was poor.

Comparative Example 5
In the same manner as in Example 1, 9 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was additionally added to the vinyl chloride polymer latex obtained in Production Example 1 to obtain a vinyl chloride polymer latex. The volume average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the content of the disproportionated potassium rosinate is 0.00. It was 4 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 6
In the same manner as in Example 1, 260 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was added to the vinyl chloride polymer latex obtained in Production Example 1 to obtain a vinyl chloride polymer latex. The volume average particle size ([MV] value) in the obtained vinyl chloride polymer latex was 0.26 μm, the concentration of vinyl chloride polymer was 35% by weight, and the content of disproportionated potassium rosinate was 12.0 parts by weight. It was.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that 214 g of the vinyl chloride polymer latex was changed. Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 7
In the same manner as in Example 1, 108 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was added to the vinyl chloride polymer latex obtained in Production Example 4 to obtain a vinyl chloride polymer latex. The obtained vinyl chloride polymer latex had a volume average particle diameter ([MV] value) of 0.10 μm, a vinyl chloride polymer concentration of 36% by weight, and a disproportionated potassium rosinate content of 4 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 3, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 8
In the same manner as in Example 1, 87 g of a 25% by weight aqueous solution of disproportionated potassium rosinate was added to the vinyl chloride polymer latex obtained in Production Example 5 to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 1.62 μm, the concentration of the vinyl chloride polymer is 40% by weight, and the content of disproportionated potassium rosinate is 4. It was 0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that the vinyl chloride polymer latex was changed to 188 g. Table 4 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability of the polyol composition was good, but the sedimentation stability was poor.

比較例９
実施例１と同じ操作で、製造例１より得られた塩化ビニルポリマーラテックスに対し、製造例８で得られた中和度０．５のイソブチレンと無水マレイン酸共重合物のナトリウム塩水溶液の２８重量％水溶液７８ｇを追加添加し、塩化ビニルポリマーラテックスを得た。得られた塩化ビニルポリマーラテックス中の塩化ビニルポリマーの積平均粒子径（［ＭＶ］値）は０．２６μｍ、塩化ビニルポリマーの濃度は３６重量％、イソブチレンと無水マレイン酸共重合物のナトリウム塩の含有量は４．０重量部だった。

Comparative Example 9
In the same manner as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the reaction of sodium salt aqueous solution of isobutylene having a neutralization degree of 0.5 obtained in Production Example 8 and a maleic anhydride copolymer. An additional 78 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The product average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 4 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 10
In the same manner as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the aqueous solution of sodium salt of isobutylene having a neutralization degree of 1.0 obtained in Production Example 9 and a maleic anhydride copolymer. An additional 78 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The product average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 4 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 11
In the same operation as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the aqueous solution of sodium salt of isobutylene having a neutralization degree of 0.8 obtained in Production Example 7 and a maleic anhydride copolymer. An additional 28 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content of was 0.4 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 4 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 12
In the same operation as in Example 1, the vinyl chloride polymer latex obtained in Production Example 1 was subjected to the aqueous solution of sodium salt of isobutylene having a neutralization degree of 0.8 obtained in Production Example 7 and a maleic anhydride copolymer. An additional 231 g of a weight% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex is 0.26 μm, the concentration of the vinyl chloride polymer is 35% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content of was 12.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that the vinyl chloride polymer latex was changed to 214 g. Table 4 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 13
28 weight of sodium salt of isobutylene having a degree of neutralization of 0.8 obtained from Production Example 7 and sodium salt of maleic anhydride copolymer with respect to the vinyl chloride polymer latex obtained from Production Example 4 in the same manner as in Example 1. An additional 10 g of a 10% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle diameter ([MV] value) in the obtained vinyl chloride polymer latex is 0.10 μm, the concentration of the vinyl chloride polymer is 36% by weight, and the content of sodium salt of isobutylene and maleic anhydride copolymer is 4 0.0 part by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1. Table 3 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability and sedimentation stability of the polyol composition were inferior.

Comparative Example 14
28 weight of sodium salt of isobutylene having a neutralization degree of 0.8 obtained from Production Example 7 and sodium salt of maleic anhydride copolymer was obtained in the same manner as in Example 1 with respect to the vinyl chloride polymer latex obtained from Production Example 5. A 78% aqueous solution was added to obtain a vinyl chloride polymer latex. The volume average particle size ([MV] value) of the vinyl chloride polymer in the obtained vinyl chloride polymer latex was 1.62 μm, the concentration of the vinyl chloride polymer was 39% by weight, and the sodium salt of isobutylene and maleic anhydride copolymer. The content was 4.0 parts by weight.

  Next, a polyol composition having a vinyl chloride polymer content of 20% by weight was obtained in the same manner as in Example 1 except that 192 g of vinyl chloride polymer latex was used. Table 4 shows the results of dispersion stability and sedimentation stability of the obtained dehydrated polyol composition. As shown in Table 4, the dispersion stability of the polyol composition was good, but the sedimentation stability was poor.

  The polyol composition of the present invention is excellent in dispersion stability and sedimentation stability, and the vinyl chloride polymer latex of the present invention can be used in the polyurethane resin manufacturing industry because it can produce the polyol composition. Have sex.

Claims (4)

For 100 parts by weight of vinyl chloride polymer having a volume average particle size ([MV] value) of 0.2 to 1.6 μm, an alkali salt of resin acid or a neutralization degree of 0.6 to 0.9 is used as a dispersant. A vinyl chloride polymer latex comprising 0.5 to 10 parts by weight of an alkali salt of a copolymer of an α-olefin and maleic anhydride. The vinyl chloride polymer latex according to claim 1, wherein the alkali salt of the resin acid is a rosin compound. Resin as a dispersant containing 5 to 40% by weight of a vinyl chloride polymer having a volume average particle size ([MV] value) of 0.2 to 1.6 μm and 100 parts by weight of the vinyl chloride polymer A polyol composition comprising 0.5 to 10 parts by weight of an alkali salt of an acid or an alkali salt of a copolymer of an α-olefin having a neutralization degree of 0.6 to 0.9 and maleic anhydride. The method for producing a polyol composition according to claim 3, wherein the vinyl chloride polymer latex according to claim 1 or 2 is mixed in a polyol and dehydrated.