JP2010031170A - Polyol composition with vinyl chloride-vinyl acetate copolymer saponified product particle dispersed therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition excellent in shelf stability, flame retardancy, and communication property. <P>SOLUTION: The polyol composition prepared includes 10-50 wt.% of a vinyl chloride-vinyl acetate copolymer saponified product particle with a vinyl acetate monomer saponification degree of 0.5 mol% or more and with a volume-average particle size ([MV] value) of 0.03-50 μm in polyol and in a dispersed state. A method for producing polyurethane resins by reacting the polyol composition with a polyisocyanate component in the presence of a catalyst and a method for producing polyurethane foams by the reaction in the presence of foaming agents are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified 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, in the conventionally known method using a polyol containing polyvinyl chloride particles, the polyvinyl chloride particles used are coarse, so that the polyvinyl chloride concentration cannot be sufficiently increased. There was a problem that the stability of the particles was insufficient and long-term storage was difficult. Also, the method of polymerizing a vinyl chloride monomer in a polyol has a problem that when the polyvinyl chloride concentration is increased, the viscosity becomes too high and handling becomes extremely difficult.

Japanese Patent Application Laid-Open No. 01-065160 Japanese Patent Application Laid-Open No. 09-059341 Japanese Patent Laid-Open No. 03-097715

  This invention is made | formed in view of said background art, The objective is to provide a polyol composition with favorable storage stability and a flame retardance.

  As a result of intensive studies to solve the above problems, the present inventor has found that a polyol composition containing saponified vinyl chloride-vinyl acetate copolymer particles in a dispersed state is contained in an amount of 10 wt% to 50 wt% in the polyol. The present inventors have found that a good polyol composition having excellent stability has been reached.

  That is, the present invention is a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles are dispersed as shown below, a production method thereof, and a polyurethane resin production method using the polyol composition.

  [1] Polyol composition containing saponified vinyl chloride-vinyl acetate copolymer particles having a saponification degree of vinyl acetate monomer of 0.5 mol% or more in a dispersed state in a polyol of 10 wt% or more and 50 wt% or less. object.

  [2] The polyol composition according to the above [1], wherein the content of the vinyl acetate monomer in the saponified vinyl chloride-vinyl acetate copolymer particles is in the range of 0.1 to 50% by weight.

  [3] The polyol composition according to the above [1] or [2], wherein the volume average particle diameter ([MV] value) of the saponified vinyl chloride-vinyl acetate copolymer particles is 0.03 μm or more and 50 μm or less.

  [4] The polyol composition according to any one of [1] to [3], wherein the viscosity is 20000 mPa · s or less.

  [5] After saponifying the vinyl chloride-vinyl acetate copolymer particles to obtain vinyl chloride-vinyl acetate copolymer saponified particles having a saponification degree of the vinyl acetate monomer of 0.5 mol% or more, The method for producing a polyol composition according to any one of the above [1] to [4], wherein the polyol composition is mixed and dispersed with a polyol.

  [6] The method for producing a polyol composition according to the above [5], wherein the content of the vinyl acetate monomer in the vinyl chloride-vinyl acetate copolymer particles is in the range of 0.1 to 50% by weight.

  [7] A method for producing a polyurethane resin in which a polyol component and a polyisocyanate component are reacted in the presence of a catalyst, wherein the polyol composition according to any one of [1] to [4] is used as the polyol component. A method for producing a polyurethane resin.

  [8] A method for producing a polyurethane foam in which a polyol component and a polyisocyanate component are reacted in the presence of a catalyst and a foaming agent, and the polyol composition according to any one of the above [1] to [4] Method for producing polyurethane foam using

  The polyol composition of the present invention has a relatively low viscosity of 20000 mPa · s or less and good handling.

  In addition, the polyol composition of the present invention is excellent in storage stability, and precipitation of vinyl chloride-vinyl acetate copolymer saponified particles is not observed even after storage for one month.

  Furthermore, when a polyurethane foam is prepared by using the polyol composition of the present invention as a part or all of the raw material polyol, improvement in flame retardancy and connectivity of the resulting foam can be expected.

  Hereinafter, the present invention will be described in detail.

  The polyol composition of the present invention is a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles are dispersed in a polyol, wherein the vinyl chloride-vinyl acetate copolymer saponified particles contain a single amount of vinyl acetate. The saponification degree of the body is 0.5 mol% or more, and the content of the saponified vinyl chloride-vinyl acetate copolymer particles is 10% by weight or more and 50% by weight or less based on the polyol composition. Features.

  In the polyol composition of the present invention, the content (concentration) of the saponified vinyl chloride-vinyl acetate copolymer particles is 10% by weight or more and 50% by weight or less with respect to the polyol composition. When the content of saponified vinyl chloride-vinyl acetate copolymer particles is less than 10% by weight, even if a polyurethane foam is prepared using this as a raw material polyol, there is a risk that imparting flame retardancy may be insufficient, When it exceeds 50% by weight, the viscosity is remarkably increased and handling may be difficult.

  In the saponified vinyl chloride-vinyl acetate copolymer particles of the present invention, the volume average particle diameter ([MV] value) is not particularly limited, but is preferably 0.03 μm or more and 50 μm or less. By setting the volume average particle diameter ([MV] value) to 0.03 μm or more, an increase in viscosity of the polyol composition and aggregation of vinyl chloride-vinyl acetate copolymer saponified particles can be suppressed. Moreover, sedimentation separation of vinyl chloride-vinyl acetate copolymer saponified particles can be suppressed by setting the volume average particle diameter ([MV] value) to 50 μm or less.

  In the present invention, the volume average particle diameter ([MV] value) of the saponified vinyl chloride-vinyl acetate copolymer particles is a particle size distribution measuring device based on the principle of a generally known laser diffraction method and dynamic light scattering method. Any apparatus can be used for measurement, 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.).

  In the present invention, the conversion ratio of acetyl groups to hydroxyl groups on the surface of saponified vinyl chloride-vinyl acetate copolymer particles (hereinafter referred to as “surface saponification degree”) is different in volume particle size and particle diameter. Since the exposure ratio of the acetyl group to the particle surface is different, it is difficult to define it in a general manner. However, for example, 30 mol% or more is preferable. By setting the surface saponification degree to 30 mol% or more, the effect of imparting dispersion stability when the vinyl chloride-vinyl acetate copolymer saponified particles are dispersed in the polyol becomes sufficient, and the particles are less likely to settle and separate.

  On the other hand, in the present invention, the conversion ratio of acetyl groups to hydroxyl groups in the entire saponified vinyl chloride-vinyl acetate copolymer particles (degree of saponification of the vinyl acetate monomer in the saponified vinyl chloride-vinyl acetate copolymer particles). Hereinafter, it may be expressed as “degree of saponification of vinyl acetate monomer”.) Since the exposure rate of acetyl groups on the particle surface differs when the volume average particle diameter ([MV] value) differs, Although it is difficult to define, it is usually 0.5 mol% or more, preferably 1 mol% or more, more preferably 2 mol% or more, if it is intentionally exemplified.

  The saponified vinyl chloride-vinyl acetate copolymer particles used in the polyol composition of the present invention are prepared by saponifying vinyl chloride-vinyl acetate copolymer particles.

  In the present invention, the vinyl chloride-vinyl acetate copolymer used for the preparation of saponified vinyl chloride-vinyl acetate copolymer particles is prepared by copolymerizing a vinyl chloride monomer and a vinyl acetate monomer. be able to. The polymerization method is not particularly limited, and vinyl chloride-acetic acid can be used as long as the volume average particle diameter ([MV] value) of the produced vinyl chloride-unsaturated vinyl copolymer particles is within the target range. Any method generally known as a method for producing vinyl copolymer particles can be used. For example, an emulsion polymerization method in which a vinyl chloride monomer and a vinyl acetate monomer are polymerized with deionized water, a surfactant, and a water-soluble polymerization initiator under gentle stirring. Seed emulsion polymerization method that uses emulsion polymerization as seed, vinyl chloride monomer and vinyl acetate monomer as deionized water, surfactant, if necessary, emulsification aid such as higher alcohol, oil soluble polymerization initiator After mixing and dispersing with a homogenizer, etc., a micro suspension polymerization method in which polymerization is performed with gentle stirring, a seed micro suspension weight in which polymerization is performed using a seed containing an oil-soluble polymerization initiator obtained by the micro suspension polymerization method Legal etc. are mentioned.

  In the present invention, the raw material monomer for forming the vinyl chloride-vinyl acetate copolymer used for the preparation of saponified vinyl chloride-vinyl acetate copolymer particles includes, in addition to the vinyl chloride monomer and the vinyl acetate monomer, An unsaturated vinyl monomer that can be copolymerized with these components may be contained. Such an unsaturated vinyl monomer is not particularly limited as long as it forms a copolymer with a vinyl chloride monomer and a vinyl acetate monomer. For example, a styrene monomer, an α-methylstyrene monomer, Styrene monomers such as hydroxystyrene monomer and chlorostyrene monomer, acrylonitrile monomers such as acrylonitrile monomer and methacrylonitrile monomer, methyl (meth) acrylate monomer, ethyl (meth) acrylate monomer, butyl (meth) acrylate (Meth) acrylic acid ester monomers such as monomers, (meth) acrylic acid monomers, (meth) acrylic acid alkali metal salt (meth) acrylamides, ethylene monomers, propylene monomers, vinylidene chloride monomers and the like. In the present invention, these unsaturated vinyl monomers may be used alone or in combination of two or more.

  Further, the content of the unsaturated vinyl monomer in the vinyl chloride-vinyl acetate copolymer is not particularly limited as long as it does not depart from the gist of the present invention. It is preferable that it is 50 weight% or less with respect to the total amount of a vinyl acetate monomer. By setting the content of the unsaturated vinyl monomer to 50% by weight or less, a copolymer having a target particle size can be easily prepared, and the effect of imparting flame retardancy can be improved. it can.

  In the present invention, the content of the vinyl acetate monomer in the vinyl chloride-vinyl acetate copolymer particles used for the preparation of the vinyl chloride-vinyl acetate copolymer saponified particles is not particularly limited. The range of 1 to 50% by weight is preferable. When the content of the vinyl acetate monomer is 0.1% by weight or more, the proportion of hydroxyl groups in the entire copolymer particles after saponification can be increased, and the dispersion stability can be improved. In addition, when the content of the vinyl acetate monomer is 50% by weight or less, the content of vinyl chloride is increased, and not only can the ability of the present invention to make the polyurethane flame-retardant can be improved. In the saponification step, the dissolution and aggregation of vinyl chloride-vinyl acetate copolymer saponified particles can be suppressed, and the yield can be improved.

  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.

  In the polyol composition of the present invention, the polyether polyol used is not particularly limited. For example, a compound having at least two active hydrogen groups (ethylene glycol, propylene glycol, glycerin, trimethylolpropane). Starting materials such as polyhydric alcohols such as pentaerythritol, amines such as ethylenediamine, alkanolamines such as ethanolamine and diethanolamine, and the like, and alkylene oxides (ethylene oxide, propylene oxide, etc.). (For example, Gunter Oertel, “Polyurethane Handbook” (1985) Hans Publishers, Inc.) Tsu), p. See method according to 42-53].

  In the polyol composition of the present invention, the polyester polyol to be used is not particularly limited, and examples thereof include those obtained from the reaction of dibasic acid and glycol, wastes from the production of nylon, trimethylolpropane, and pentane. Examples include erystole waste, phthalate polyester waste, polyester polyols obtained by treating and treating waste [for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. See description of 117. ].

  In the polyol composition of the present invention, the polymer polyol to be used is not particularly limited. For example, the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) are used. Examples include polymer polyols reacted in the presence of a radical polymerization catalyst.

  In the polyol composition of the present invention, the flame retardant polyol used is not particularly limited. For example, a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, epichlorohydrin, or trichlorobutylene oxide. Examples thereof include halogen-containing polyols and phenol polyols obtained by ring-opening polymerization.

Further, as the polyol composition of the present invention, Sanniks (trade name, manufactured by Sanyo Kasei Kogyo Co., Ltd.), Exenol (trade name, manufactured by Asahi Glass Co., Ltd.), Act Coal (product) Name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), VORANOL (trade name, manufactured by DOW), etc. can be used In the polyol composition of the present invention, a polyol having an average hydroxyl value in the range of 20 to 1000 mgKOH / g is used. However, when a soft polyurethane resin or a semi-rigid polyurethane resin is produced, an average hydroxyl value is in the range of 20 to 100 mgKOH / g. When a rigid polyurethane resin is produced, an average hydroxyl value is 100 to 800 mgKOH / g. Those in the range are preferably used.

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

  In the method for producing the polyol composition of the present invention, vinyl chloride-vinyl acetate copolymer particles are saponified, acetyl groups are converted to hydroxyl groups, and the saponification degree of the vinyl acetate monomer is 0.5 mol% or more. The vinyl-vinyl acetate copolymer particles are mixed, then mixed with a polyol, and dispersed.

  In the present invention, the method for saponifying vinyl chloride-vinyl acetate copolymer particles is not particularly limited, and for example, a conventionally known method for producing polyvinyl alcohol by saponifying a vinyl acetate resin can be applied.

  As a specific saponification method, vinyl chloride-vinyl acetate copolymer particles are dispersed in water, and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxylated water such as ammonia water and quaternary amine are used. A method of adding an alkali component such as a product and heating at room temperature to 70 ° C. for a predetermined time can be exemplified.

  The amount of the alkali component added in the saponification step described above is not particularly limited as long as it is sufficient to convert the acetyl group to a hydroxyl group, but is not limited in the vinyl chloride-vinyl acetate copolymer particles. The molar ratio of to the amount of vinyl acetate monomer is usually 0.1 or more, preferably 0.5 or more, more preferably equivalent. Even if the amount of the alkali component is added more than the same amount, the effect is small, and the drug cost of the excess alkali component is increased, and more acid is required for the neutralization treatment, which is not preferable.

  Moreover, aggregation of a vinyl chloride-vinyl acetate copolymer saponified particle can be suppressed by heating temperature to 70 degrees C or less.

  Since the heating time varies depending on the temperature at the time of heating, it is difficult to define it generally. However, if it is purposely specified, the time until the saponification of the acetyl groups on the surface of the vinyl chloride-vinyl acetate copolymer particles sufficiently proceeds. It is preferable to apply 8 hours or more at room temperature, 3 hours or more at 50 ° C., and 1 hour or more at 70 ° C.

  The saponified vinyl chloride-vinyl acetate copolymer particles after saponification are in a state of being dispersed in water and contain unreacted alkali components. Therefore, it is necessary to first remove the unreacted alkali component by filtration or the like, or to perform a neutralization treatment. When an unreacted alkali component is removed or mixed with a polyol without carrying out a neutralization treatment and then subjected to a dispersion treatment, the alkali component may react with vinyl chloride to form a polyene and cause coloring.

  If the particle size of the saponified vinyl chloride-vinyl acetate copolymer particles after saponification is relatively large and filtration is possible, the saponified vinyl chloride-vinyl acetate copolymer saponified in water after saponification The compound particles are filtered, washed with water, and dried to remove unreacted alkali components and water, and then mixed with the polyol. The drying temperature at this time is preferably room temperature to 70 ° C., more preferably room temperature to 60 ° C. By setting the drying temperature to 70 ° C. or lower, the aggregation of the particles becomes weak and a good dispersion can be obtained.

  In addition, when the particle size of the saponified vinyl chloride-vinyl acetate copolymer particles after saponification is relatively small and filtration is difficult, neutralization treatment of unreacted alkali components is performed and spray drying is performed. The water can be removed by mixing with the polyol. Since the spray drying conditions at this time vary depending on the spray drying apparatus used, it is difficult to define them in general. Is preferred. When the temperature is higher than this temperature, the obtained dried vinyl chloride-vinyl acetate copolymer particles are likely to aggregate due to heat, and it may be difficult to obtain a good dispersion.

  In the present invention, the dispersion treatment of the mixture of vinyl chloride-vinyl acetate copolymer saponified particles and polyol is not particularly limited, and various conventionally known dispersion methods can be used. As a specific dispersion method, T.W. K. Examples thereof include high-speed emulsification / dispersing machines such as Homodispa (trade name, manufactured by Primix Co., Ltd.), and ball milling. Moreover, after neutralizing the unreacted alkali component in the mixture of saponified vinyl chloride-vinyl acetate copolymer saponified particles and water after saponification, this is mixed with polyol to remove the remaining water. A method can also be illustrated.

  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, the inclusion of vinyl chloride polymer particles and / or vinyl chloride-unsaturated vinyl copolymer particles with respect to the polyol used (including the polyol in the polyol composition of the present invention). The rate is preferably 10% by weight or more, and more preferably 20% by weight or more. When the content of the vinyl chloride polymer particles and / or the vinyl chloride-unsaturated vinyl copolymer particles is less than 10% by weight, the vinyl chloride polymer particles and / or Since the content of vinyl chloride-unsaturated vinyl copolymer particles is insufficient, the flame retardancy imparting effect may be insufficient, and the polyurethane foam hardness expected as an effect of adding polyol is improved. And there is a risk that the improvement of communication will be insufficient.

  In the method for producing a polyurethane resin of the present invention, the polyisocyanate used as an 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. It is done. 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 or a tertiary amine catalyst is used. Quaternary ammonium salt catalysts are publicly listed.

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

  The carboxylic acid metal salt may be a conventionally known metal salt, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  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, 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, or ethylenediamine and xylylene. Examples include polyamines such as range amine and methylene bisorthochloroaniline.

  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. As the polyurethane foaming machine, high-pressure, low-pressure and spray-type devices can be used.

  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, and rigid polyurethane foam. The polyurethane resin production method of the present invention includes a flexible polyurethane foam car sheet and semi-rigid polyurethane used as automobile interior materials. 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, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. See description of 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. Oertel, "Polyurethane Handbook" (1985 edition) Hanser Publishers (Germany), p. 223-233, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 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 from the raw materials used and the physical properties of the foam.

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, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 224-283. ]. 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.

  Hereinafter, the present invention will be specifically described with reference to examples.

  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 was measured with a B-type viscometer according to JIS K-1557-5.

  The oxygen index was measured according to ASTM D2863-77.

  The evaluation of the connectivity was made by mixing the polyol composition of the present invention and various raw materials, adding isocyanate and mixing at 6000 rpm for 5 seconds, and then adjusting the temperature to 60 ° C. in advance of 250 mm in length × 250 mm in width × 80 mm in height. Pour into the mold, cover and cure for 5 minutes to create a test polyurethane foam. Using the 200φ disc, the polyurethane foam is repeatedly compressed to a compression ratio of 65%. The difference in force required for the second round was used to evaluate the connectivity. If the communication is good, the difference between the force required for the first compression and the force required for the second compression is reduced.

Example 1.
44. Vinyl chloride-vinyl acetate copolymer particles (vinyl acetate monomer content 5% by weight, volume average particle size ([MV] value) 1.5 μm) obtained by seed microsuspension polymerization method are 44. 2 L of latex solution containing 5% by weight was put into a separable flask, and vinyl acetate monomer and an equimolar amount of sodium hydroxide were added. This solution was heated at 50 ° C. for 12 hours to saponify the vinyl acetate monomer on the particle surface. The conversion ratio of acetyl groups to hydroxyl groups was determined from the amount of sodium hydroxide consumed. As a result, 2.0 mol% of acetyl groups were converted to hydroxyl groups (the degree of saponification of the vinyl acetate monomer was 2.0 mol). %). As a result of obtaining the conversion ratio of the acetyl group to the hydroxyl group on the particle surface by geometric calculation, 100 mol% of the acetyl group in the particle surface was converted to the hydroxyl group (the surface saponification degree of the vinyl acetate monomer was 100). Mole%) was found.

  Excess sodium hydroxide in the latex solution containing the saponified vinyl chloride-vinyl acetate copolymer saponified particles was neutralized by adding acetic acid. The latex solution after neutralization is dehydrated by spray drying at an inlet air temperature of 110 ° C. and an exhaust air temperature of 50 ° C., and a saponified vinyl chloride-vinyl acetate copolymer in which the acetyl groups on the particle surface are converted to hydroxyl groups. A powder of particles was obtained.

  200 g of the obtained powder was mixed with 200 g of a polyol [(trade name) Voranol 360, manufactured by Dow, polyether polyol, OH number 360], and then a high-speed emulsifier / disperser [(trade name) T.A. K. Homodispa, manufactured by Primix Co., Ltd.] was used for 15 minutes, and then 100 g of the same kind of polyol was added and mixed for 3 minutes.

  By the above operation, a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles were dispersed was obtained. The concentration (content) of the saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 40% by weight, and the volume average particle size ([MV] value) was 1.8 μm. Moreover, the viscosity of the obtained polyol composition was 9000 mPa · s, and as a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a rigid polyurethane foam was prepared using the obtained polyol composition. The polyurethane foam was prepared by 25 g of a polyol composition, 25 g of a commercially available polyol (Voranol 360), a foam stabilizer [(trade name) L5420, manufactured by Nihon Unicar Co., Ltd.] 1 g, 2.5 g of water, a catalyst [(trade name) TOYOCAT- After mixing 1.2 g of MR, manufactured by Tosoh Corporation, tetramethylhexanediamine], isocyanate [(trade name) Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd., Crude MDI, NCO% = 30.8%] It added so that an isocyanate index might be set to 110, and after stirring at 6000 rpm for 6 second, it injected and implemented in the 2L polyethylene cup. The obtained rigid polyurethane foam had an oxygen index of 19.2%.

Example 2
75 g of the powder of saponified vinyl chloride-vinyl acetate copolymer particles obtained in Example 1 was mixed with 75 g of a commercially available polyol (Voranol 360). K. Dispersion treatment was performed for 15 minutes using a homodispa, and then 350 g of the same commercially available polyol was further added and mixed for 3 minutes.

  By the above operation, a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles were dispersed was obtained. The concentration of the vinyl chloride-vinyl acetate copolymer particles in the composition was 15% by weight, and the volume average particle size ([MV] value) was 1.7 μm. Moreover, the viscosity of the obtained polyol composition was 5200 mPa · s. As a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a polyurethane foam was prepared in the same manner as in Example 1 except that 50 g of the obtained polyol composition and 0 g of a commercially available polyol were used. The obtained rigid polyurethane foam had an oxygen index of 18.6%.

Example 3 FIG.
44. Vinyl chloride-vinyl acetate copolymer particles (vinyl acetate monomer content 5% by weight, volume average particle size ([MV] value) 1.5 μm) obtained by seed microsuspension polymerization method. 2 L of latex solution containing 5% by weight was placed in a separable flask, and vinyl acetate monomer and an equimolar amount of sodium hydroxide were added. This solution was heated at 50 ° C. for 30 minutes to saponify the vinyl acetate monomer on the particle surface. About the obtained vinyl chloride-vinyl acetate copolymer saponified particles, the saponification degree of the vinyl acetate monomer and the surface saponification degree were determined in the same manner as in Example 1. As a result, the saponification degree of the vinyl acetate monomer was 1.0 mol% and the degree of surface saponification were 50 mol%.

  Using the obtained latex solution containing the saponified vinyl chloride-vinyl acetate copolymer particles, the same operation as in Example 1 was carried out to disperse the saponified vinyl chloride-vinyl acetate copolymer particles. Got. The concentration of the saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 40% by weight, and the volume average particle size ([MV] value) of the saponified vinyl chloride-vinyl acetate copolymer particles was 2. It was 0 μm. Moreover, the viscosity of the obtained polyol composition was 9800 mPa · s. As a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a rigid polyurethane foam was prepared by performing the same operation as in Example 1 except that the obtained polyol composition was used. The obtained rigid polyurethane foam had an oxygen index of 19.2%.

Example 4
Vinyl chloride-vinyl acetate copolymer particles (vinyl acetate monomer content 2.5% by weight, volume average particle size ([MV] value) 1.5 μm) obtained by seed microsuspension polymerization method 2 L of latex solution containing 44.0% by weight was placed in a separable flask, and vinyl acetate monomer and an equimolar amount of sodium hydroxide were added. This solution was heated at 50 ° C. for 12 hours to saponify the vinyl acetate monomer on the particle surface. About the obtained vinyl chloride-vinyl acetate copolymer saponified particles, the saponification degree of the vinyl acetate monomer and the surface saponification degree were determined in the same manner as in Example 1. As a result, the saponification degree of the vinyl acetate monomer was The surface saponification degree was 2.0 mol% and 100 mol%.

  Using the obtained latex solution containing the saponified vinyl chloride-vinyl acetate copolymer particles, the same operation as in Example 1 was carried out to disperse the saponified vinyl chloride-vinyl acetate copolymer particles. Got. The concentration of the saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 40% by weight, and the volume average particle size ([MV] value) was 2.5 μm. Moreover, the viscosity of the obtained polyol composition was 11000 mPa · s. As a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a rigid polyurethane foam was prepared by performing the same operation as in Example 1 except that the obtained polyol composition was used. The obtained rigid polyurethane foam had an oxygen index of 19.1%.

Comparative Example 1
A latex solution containing 44.5 wt% of vinyl chloride-vinyl acetate copolymer particles (vinyl acetate monomer content of 5 wt%, volume average particle size ([MV] value) 1.5 μm) Dehydration was performed by spray drying at 110 ° C. and an exhaust air temperature of 50 ° C. to obtain a powder of vinyl chloride-vinyl acetate copolymer particles (degree of saponification of vinyl acetate monomer of 0 mol%).

  After mixing 200 g of the obtained powder with 200 g of a commercially available polyol (Voranol 360), T.W. K. Dispersion treatment was performed for 15 minutes using a homodispa, and then 100 g of the same polyol was further added and mixed for 3 minutes.

  By the above operation, a polyol composition in which vinyl chloride-vinyl acetate copolymer particles were dispersed was obtained. The concentration of the vinyl chloride-vinyl acetate copolymer particles in this composition was 40% by weight, and the volume average particle diameter ([MV] value) was 3.0 μm. Moreover, the viscosity of the obtained polyol composition was 13000 mPa · s, and as a result of conducting a storage test for one month, sediment was confirmed.

  Next, a rigid polyurethane foam was prepared by performing the same operation as in Example 1 except that the obtained polyol composition was used. The obtained rigid polyurethane foam had an oxygen index of 19.2%.

Comparative Example 2
275 g of the powder of saponified vinyl chloride-vinyl acetate copolymer particles obtained in Example 1 was mixed with 225 g of a commercially available polyol (Voranol 360). K. Dispersion treatment was performed for 15 minutes using a homodispa.

  By the above operation, a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles were dispersed was obtained. The concentration of saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 55% by weight, and the volume average particle size ([MV] value) was measured and found to be 2.4 μm. Moreover, the viscosity of the obtained polyol composition was 35000 mPa · s, and as a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a rigid polyurethane foam was prepared in the same manner as in Example 1 except that 18.2 g of the obtained polyol composition and 31.8 g of a commercially available polyol were used. The obtained rigid polyurethane foam had an oxygen index of 19.1%.

Comparative Example 3
50 g of the saponified vinyl chloride-vinyl acetate copolymer particles obtained in Example 1 were mixed with 50 g of a commercially available polyol (Voranol 360). K. Dispersion treatment was performed for 15 minutes using a homodispa. Thereafter, 50 g of this mixture was collected, and another 450 g of the same polyol was added and mixed for 3 minutes.

  By the above operation, a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles were dispersed was obtained. The concentration of saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 5% by weight, and the volume average particle size ([MV] value) was 2.0 μm. Moreover, the viscosity of the obtained polyol composition was 4000 mPa · s. As a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a rigid polyurethane foam was prepared by performing the same operation as in Example 2 except that the obtained polyol composition was used. The obtained rigid polyurethane foam had an oxygen index of 18.1%.

Comparative Example 4
2 L of a latex solution containing 44.8% by weight of vinyl chloride polymer particles (volume average particle diameter ([MV] value) 1.5 μm) is placed in a separable flask, and further 5 mol% of hydroxylated with respect to the vinyl chloride component. Sodium was added. This solution was heated at 50 ° C. for 12 hours. The amount of sodium hydroxide consumed was 0 mol%, and it was found that sodium hydroxide and vinyl chloride polymer particles did not react.

  The sodium hydroxide content in the latex solution containing the vinyl chloride particles after the above operation was neutralized by adding acetic acid. The latex solution after the neutralization treatment is dehydrated by spray drying using a laboratory spray dryer (Okawara Kako Co., Ltd., L-8 type spray dryer) under conditions of an inlet air temperature of 110 ° C and an exhaust air temperature of 50 ° C. And a powder of vinyl chloride polymer particles was obtained.

  About the obtained powder, operation similar to Example 1 was performed and the polyol composition in which the vinyl chloride polymer particle was disperse | distributed was obtained. The concentration of the vinyl chloride polymer particles in the composition was 40% by weight, and the volume average particle size ([MV] value) was 3.0 μm. Moreover, the viscosity of the obtained polyol composition was 15000 mPa · s, and as a result of conducting a storage test for one month, sediment was confirmed.

  Next, a rigid polyurethane foam was prepared by performing the same operation as in Example 1 except that the obtained polyol composition was used. The obtained rigid polyurethane foam had an oxygen index of 19.3%.

Comparative Example 5
A rigid polyurethane foam was prepared in the same manner as in Example 1 except that the polyol composition of the present invention was not used and the commercially available polyol was changed to 50 g. The obtained rigid polyurethane foam had an oxygen index of 17.9%.

  The result of Examples 1-4 and Comparative Examples 1-5 is combined with Table 1, and is shown.

表１から明らかなとおり、本発明のポリオール組成物は保存安定性が優れており、これを用いて硬質ポリウレタンフォームを調製した場合、難燃性が向上する。

As is apparent from Table 1, the polyol composition of the present invention is excellent in storage stability, and when a rigid polyurethane foam is prepared using this, the flame retardancy is improved.

Example 5 FIG.
200 g of the powder of the saponified vinyl chloride-vinyl acetate copolymer particles obtained in Example 1 was used as a polyol [(trade name) Sannix FA-703, manufactured by Sanyo Chemical Industries, Ltd., glycerin polyether polyol, OH value. : 32.9 KOH / g] after mixing with 200 g, K. Dispersion treatment was performed for 15 minutes using a homodispa, and then 100 g of the same polyol was further added and mixed for 3 minutes.

  By the above operation, a polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles were dispersed was obtained. The concentration of saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 40% by weight, and the volume average particle size ([MV] value) was 1.8 μm. Moreover, the viscosity of the obtained polyol composition was 4600 mPa · s. As a result of conducting a storage test for one month, no sediment was confirmed.

  Next, a flexible polyurethane foam was prepared using the obtained polyol composition. The flexible polyurethane foam was prepared by 41.67 g of a vinyl chloride-vinyl acetate copolymer polymer polyol composition, 125.01 g of a commercially available polyol (Sanix FA-703), a commercially available polyol [(trade name) Voranol CP1421, manufactured by Dow Chemical Company. , 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, After mixing 1.8 g of water and 1.44 g of catalyst [(trade name) TEDA-L33, manufactured by Tosoh Corporation, triethylenediamine], isocyanate [(trade name) Coronate 1106, manufactured by Nippon Polyurethane Industry Co., Ltd., Polymeric MD In addition the system isocyanates, NCO% = 31.7%] and so index is 98, the mixture was stirred for 5 seconds at 6500 rpm, was performed and poured into a mold. As a result of evaluating the connectivity of the obtained flexible polyurethane foam, it was 280 N.

Comparative Example 6
A polyol composition in which vinyl chloride-vinyl acetate copolymer saponified particles were dispersed by performing the same operation as in Example 5 except that the vinyl chloride-vinyl acetate copolymer saponified particles obtained in Comparative Example 1 were used. I got a thing. The concentration of saponified vinyl chloride-vinyl acetate copolymer particles in this composition was 40% by weight, and its volume average particle size ([MV] value) was 2.5 μm. Moreover, the viscosity of the obtained polyol composition was 5300 mPa * s, and the sediment was confirmed as a result of performing the storage test for 1 month.

  Next, a flexible polyurethane foam was prepared by performing the same operation as in Example 5 except that the obtained polyol composition was used. As a result of evaluating the connectivity of the obtained flexible polyurethane foam, it was 804 N.

  The results of Example 5 and Comparative Example 6 are also shown in Table 2.

表２から明らかなとおり、本発明のポリオール組成物は保存安定性が優れており、これを用いて軟質ポリウレタンフォームを調製した場合、連通性が向上する。

As is clear from Table 2, the polyol composition of the present invention has excellent storage stability, and when a flexible polyurethane foam is prepared using this, the connectivity is improved.

Claims (8)

A polyol composition containing vinyl chloride-vinyl acetate copolymer saponified particles having a saponification degree of a vinyl acetate monomer of 0.5 mol% or more in a dispersed state in a polyol of 10 wt% or more and 50 wt% or less. 2. The polyol composition according to claim 1, wherein the content of the vinyl acetate monomer in the saponified vinyl chloride-vinyl acetate copolymer particles is in the range of 0.1 to 50% by weight. 3. The polyol composition according to claim 1, wherein the volume average particle diameter ([MV] value) of the vinyl chloride-vinyl acetate copolymer saponified particles is 0.03 μm or more and 50 μm or less. . The polyol composition according to any one of claims 1 to 3, wherein the viscosity is 20000 mPa · s or less. After saponifying the vinyl chloride-vinyl acetate copolymer particles to obtain vinyl chloride-vinyl acetate copolymer saponified particles having a saponification degree of the vinyl acetate monomer of 0.5 mol% or more, the particles are mixed with the polyol. The method for producing a polyol composition according to any one of claims 1 to 4, wherein the dispersion treatment is performed. The method for producing a polyol composition according to claim 5, wherein the content of the vinyl acetate monomer in the vinyl chloride-vinyl acetate copolymer particles is in the range of 0.1 to 50% by weight. A method for producing a polyurethane resin in which a polyol component and a polyisocyanate component are reacted in the presence of a catalyst, wherein the polyol composition according to any one of claims 1 to 4 is used as the polyol component. A method for producing a polyurethane resin. A method for producing a polyurethane foam in which a polyol component and a polyisocyanate component are reacted in the presence of a catalyst and a foaming agent, wherein the polyol composition according to any one of claims 1 to 4 is used as the polyol component. A process for producing a polyurethane foam characterized by