JP2009102566A - Polyurethane vibration-damping material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane-cured material without having the problems of waterproofness and moist heat resistance, and capable of exhibiting an excellent vibration damping performance in a wide temperature range. <P>SOLUTION: This composition is provided by containing (A) a conjugated diene-based polymer having ≤50% 1,4-bonding rate and having a hydroxy group at its molecular terminal, (B) a conjugated diene-based polymer having ≥60% 1,4-bonding rate and having the hydroxy group at the molecular terminal and (C) a polyisocyanate compound, and the cured material prepared by curing the composition is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to vibration control / vibration / sound insulation / sound absorption / soundproof materials for ceiling devices and interior walls, bridges and roads of automobiles, railway vehicles, airplanes, etc .; Materials; Shock absorbers (particularly materials that make up viscoelastic dampers that absorb shock displacement and vibration of skeletal structure forming materials in the building field); Seismic isolation materials; CD players and other very sensitive acoustic and precision equipment The present invention relates to a polyurethane damping material used as a vibration damping material.

  Conventionally, as a urethane-based vibration damping material, an ether-based polyol or an ester-based polyol (for example, see Patent Document 1), polybutadiene or polyisoprene containing a hydroxyl group at a molecular terminal, polyoxypropylene glycol, and A cured product having a low hardness and rebound resilience obtained by adding a polyol compound such as castor oil to a prepolymer obtained by reacting isocyanate and curing it in the presence of a catalyst, and having excellent water resistance (for example, , Patent Document 2), a damping material having a maximum loss tangent at −50 to 120 ° C. of 0.5 or more obtained by reacting a polyhydroxy saturated hydrocarbon polymer and a hydroxyl group-containing compound with an isocyanate compound (patent) Document 3) is known.

Japanese Patent Laid-Open No. 10-330451 JP-A-57-080421 Japanese Patent Laid-Open No. 62-190215

  However, the polyurethane compound described in Patent Document 1 has a problem of low water resistance and moist heat resistance. In the inventions described in Patent Documents 2 and 3, there is no problem of such water resistance and heat and humidity resistance, but this is not satisfactory in terms of vibration damping performance in a wide temperature range, and there is room for further improvement.

  As a result of intensive studies focusing on the above problems, the present inventors have cured a composition containing a polyisocyanate compound and a combination of a conjugated diene polymer having a hydroxyl group at the molecular end of a specific 1,4 bond rate. The present invention was completed by finding that the cured polyurethane (damping material) obtained in this way has no problem of water resistance and moist heat resistance and exhibits excellent vibration damping performance in a wide temperature range.

That is, the present invention
[1] (A) Conjugated diene polymer having a 1,4 bond ratio of 50% or less and having a hydroxyl group at the molecular terminal and (B) A conjugated diene having a 1,4 bond ratio of 60% or more and having a hydroxyl group at the molecular terminal -Based polymer, and (C) a composition containing a polyisocyanate compound,
[2] The composition according to [1], further containing 0 to 500 parts by mass of process oil with respect to 100 parts by mass in total of the component (A) and the component (B),
[3] The composition according to [1] or [2], further containing 0 to 1000 parts by weight of a bituminous substance with respect to 100 parts by weight in total of the component (A) and the component (B),
[4] The composition according to any one of [1] to [3], further containing a filler,
[5] In any one of the above [1] to [4], the conjugated diene polymer in the components (A) and (B) is a polymer composed of butadiene and / or isoprene or a hydrogenated product thereof, respectively. The composition described,
[6] The blending ratio of the component (A) and the component (B) is (A) :( B) = 95: 5 to 5:95, as described in any one of the above [1] to [5] Composition of the
[7] Ratio (NCO / OH) of the number of isocyanate groups (NCO) of component (C) and the total number of hydroxyl groups (OH) of components (A) and (B) is 0.5 to 2.5. The composition according to any one of [1] to [6],
[8] A polyurethane cured product obtained by curing the composition according to any one of [1] to [7],
[9] A polyurethane damping material obtained by curing the composition according to any one of [1] to [7],
Is to provide.

  According to the present invention, the structure is excellent in water resistance, hydrolysis resistance and rubber elasticity, (1) the maximum value of tan δ is 1.0 or more, and (2) from a low temperature (around −40 ° C.) to a high temperature (100 Over a wide temperature range of 0.1 ° C.), tan δ is 0.1 or more, excellent vibration damping at room temperature (about 23 ° C.), and a polyurethane cured product with a wide temperature range that maintains high vibration damping performance is obtained. It is done.

  The present invention includes (A) a 1,4 bond ratio (1,4 bond repeating unit content) of 50% or less and a conjugated diene polymer having a hydroxyl group at the molecular end and (B) a 1,4 bond ratio of 60%. By curing the conjugated diene-based polymer having a hydroxyl group at the molecular terminal and the (C) polyisocyanate compound, a polyurethane cured product is obtained.

  The conjugated diene polymer is a polymer of a monomer having a conjugated diene bond at the molecular end, and the monomer having a conjugated diene bond at the molecular end is preferably a monomer having 4 to 22 carbon atoms, more preferably 4 carbon atoms. -8 monomers, such as 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, cyclopentadiene, and the like. These may be used individually by 1 type and may use 2 or more types together. In addition, a copolymerizable monomer such as ethylene, propylene, butene, styrene, α-methylstyrene, and p-methylstyrene may be used in combination with the previous monomer as long as the curing of the present invention is not impaired.

As a method for producing component (A), a conjugated diene polymer having a hydroxyl group at the molecular terminal having a 1,4 bond ratio of 50% or less, preferably 15 to 50%, a diene monomer is subjected to anionic polymerization and a living polymer. And a method of reacting a monoepoxy compound and the like.
A commercially available component (A) may be used. Examples of commercially available products include “Krasol LBH-P2000” (component: polybutadiene polyol, number average molecular weight 2100, 1,4 bond ratio 35%, manufactured by Sartomer), “Krasol LBH-P3000” (component: polybutadiene polyol, number average) Molecular weight 3000, 1,4 bond ratio 35%, manufactured by Sartomer), “Krasol LBH-P5000” (component: polybutadiene polyol, number average molecular weight 4800, 1,4 bond ratio 35%, manufactured by Sartomer), “Krasol HLBH- "P2000" (component: hydrogenated polybutadiene polyol, number average molecular weight 2100, manufactured by Sartomer), "Krasol HLBH-P3000" (component: hydrogenated polybutadiene polyol, number average molecular weight 3000, manufactured by Sartomer) Etc., and the like.

Component (B), which is a conjugated diene polymer having a hydroxyl group at the molecular terminal having a 1,4 bond ratio of 60% or more, preferably 70% or more, is prepared by using a polymerization initiator such as hydrogen peroxide as a diene. And a method of radical polymerization of a monomer.
A commercially available component (B) may be used. Examples of commercially available products include “Poly bd R-45HT” (component; polybutadiene polyol, number average molecular weight 2800, 1,4 bond ratio 80%, manufactured by Idemitsu Kosan Co., Ltd.), “Poly bd R-15HT” (component; polybutadiene). Polyol, number average molecular weight 1200, 1,4 bond rate 80%, manufactured by Idemitsu Kosan Co., Ltd., "Epol" (registered trademark, component; hydrogenated polyisoprene polyol, number average molecular weight 2500, 1,4 bond rate 80%, Idemitsu Kosan Co., Ltd.).

  The number average molecular weight of the conjugated diene polymer having a hydroxyl group at the molecular end is preferably 200 to 20000, more preferably 500 to 20000, still more preferably 500 to 10,000. It is especially preferable that it is -5000. As described above, in the present invention, although it is described as a diene polymer, it may be substantially an oligomer. However, when the number average molecular weight is 500 or more, higher vibration damping performance tends to be stably obtained over a wide range of temperatures. If it is in the above range, the viscosity becomes appropriate, and the workability is high and advantageous. Further, the cured product obtained in the present invention does not become too hard, and rubber elasticity can be maintained.

  The number of terminal hydroxyl groups of the conjugated diene polymer having a hydroxyl group at the molecular end is preferably 1.7 to 4 and more preferably 1.8 to 3 per molecule of the conjugated diene polymer. The number is preferably 1.9 to 2.5. Within this range, there is little stickiness, and there is no problem of gelation of the composition, and a cured product having an appropriate hardness can be obtained after curing. In addition, not only the molecular terminal but also the inside of the molecule may have a hydroxyl group.

  The blending ratio of component (A) to component (B) is preferably (A) :( B) = 95: 5 to 5:95, more preferably 90:10 to 40:60, particularly preferably 90:10. 60:40. Within this range, the maximum value of tan δ is 1.0 or more, and tan δ is 0.15 or more over a wide temperature range from about −40 ° C. to 100 ° C., and around room temperature (about 15 to 25 Is preferable because a cured polyurethane (damping material) excellent in vibration damping performance at a temperature of 0 ° C. can be obtained.

In addition to the components (A) and (B), the composition of the present invention may be blended with a polyol compound and / or a polyamine compound as long as the effects of the present invention are not impaired. Examples of the polyol compound include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,2-pentanediol. 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, castor oil, hydrogenated castor oil, etc. However, it is not limited to these. Examples of the polyamine compound include aliphatic polyamines such as hexamethylenediamine and polyoxypropylene polyamine, alicyclic polyamines such as 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, and 3,3′-dichloro-4. , 4′-diaminodiphenylmethane, 3,5-diethyltoluene-2,4-diamine, aromatic polyamines such as 3,5-diethyltoluene-2,6-diamine, and the like.
When the polyol compound and / or the polyamine compound are blended, the blending amount thereof is such that the total number of active hydrogens of the polyol compound and the polyamine compound is 0.1 with respect to the total number of hydroxyl groups of the components (A) and (B). It is preferable to be less than or equal to twice, and more preferably less than or equal to 0.05 times.

The component (C) polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups that can react with the hydroxyl groups of components (A) and (B). Examples of such polyisocyanate compounds include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenyl. Aromatic polyisocyanates such as methane triisocyanate, tris (isocyanatephenyl) thiophosphate, isopropylbenzene-2,4-diisocyanate;
Aliphatic-aromatic polyisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI) (polyisocyanate in which an isocyanate group is bonded to an aromatic ring via an aliphatic hydrocarbon, that is, aromatic in the molecule A polyisocyanate having no isocyanate group directly bonded to the aromatic ring);

  Hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, trimethylhexa Aliphatic polyisocyanates such as methylene diisocyanate; transcyclohexane-1,4-diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl Examples include alicyclic polyisocyanates such as xylylene diisocyanate. That.

  In addition, cyclized trimer (isocyanurate-modified product) of the polyisocyanate compound, burette-modified product, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol, trimethylolpropane, polyether polyol, Polyol compounds such as polymer polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol, polyalkadiene polyol, hydride of polyalkadiene polyol, partially saponified ethylene-vinyl acetate copolymer, castor oil-based polyol, and the above polyisocyanate An addition reaction product with a compound can be used.

Furthermore, the isocyanate groups of these polyisocyanate compounds are blocked with phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite, boric acid, etc. A so-called blocked isocyanate compound blocked with an agent can also be used.
Moreover, such polyisocyanate compounds are commercially available, and commercially available products may be used. Examples of commercially available products include “Millionate MR” (component: polyfunctional diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.), “Millionate MTL” (component: carbodiimidized diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.), Module W "(component; hydrogenated diphenylmethane diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.).
A component (C) polyisocyanate compound may be used individually by 1 type, and may use 2 or more types together. The compounding amount of the component (C) is such that the relationship between the number of isocyanate groups (NCO) contained in the component (C) and the total number of hydroxyl groups (OH) of the components (A) and (B) is NCO / OH = It is preferably 0.5 to 2.5, more preferably 0.5 to 1.5, and particularly preferably 0.7 to 1.2. However, when the composition of the present invention is prepared by the prepolymer method described later, it is preferable that NCO / OH = 1.7 to 25 at the stage of producing the prepolymer, and the composition of the present invention is prepared from the prepolymer. In the preparation step, the above ranges can be referred to as preferred.

Moreover, in order to accelerate hardening, you may mix | blend a catalyst with the composition of this invention. Examples of such a catalyst include triethylenediamine, tetramethylguanidine, N, N, N′N′-tetramethylhexane-1,6-diamine, N, N, N′N ″ N ″ -pentamethyldiethylenetriamine, bis (2 Tertiary amines such as -dimethylaminoethyl) ether, 1,2-dimethylimidazole, N-methyl-N '-(2-dimethylamino) ethylpiperazine, diazabicycloundecene; carboxylic acids of the tertiary amines Salt; stannous octoate of the tertiary amine, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marker peptide, dioctyltin thiocarboxylate, phenylmercurypropionic acid Organometallic compounds such as salts and octenoates Etc.
When the catalyst is blended, the blending amount is preferably 10 parts by mass or less, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the components (A) and (B). Preferably, it is 0.01-0.5 mass part. If it is this range, since gelatinization by a local abnormal reaction does not occur easily, it is preferable.

  Furthermore, the composition of the present invention contains fillers such as inorganic fillers / organic fillers, bituminous substances, process oils, and other additives as “other components” within a range that does not impair the effects of the invention. You may let them.

Examples of the inorganic filler include mica, zinc, aluminum, copper, nickel, glass sphere, glass flake, glass fiber, carbon black (channel black, furnace black, acetylene black, thermal black), carbon fiber, graphite, asbestos, and kaolin. Clay, wax stone clay, talc, scumite, cryolite, wollastonite, diatomaceous earth, slate powder, whiting, feldspar powder, mica, gypsum, quartz powder, fine silica, attapulgite, sericite, volcanic ash, meteorite, Silica, alumina, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, titanic acid Potassium, boron nitride, boron nitrite, molybdenum disulfide, and the like.
When the inorganic filler is blended, the blending amount is preferably 400 parts by mass or less, more preferably 200 parts by mass or less, with respect to 100 parts by mass in total of the components (A) and (B). More preferably, it is 40 parts by mass or less. Within this range, the vibration damping performance (Tan δ) can be improved while maintaining the rubber elasticity of the polyurethane cured product.

Examples of organic fillers include rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, and wood powder; natural fibers such as cotton, hemp, wool, and silk; synthesis of nylon, polyester, vinylon, acetate, acrylic, and the like Fiber: Polyethylene, polypropylene, polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), epoxy Examples thereof include synthetic resin powders such as resins and phenol resins, and granules.
When the organic filler is blended, the blending amount is preferably 300 parts by mass or less, more preferably 30 to 250 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Preferably, it is 50-200 mass parts. Within this range, the vibration damping performance (Tan δ) can be improved while maintaining the rubber elasticity of the polyurethane cured product.

Examples of the bitumen include natural asphalt; petroleum asphalt such as straight asphalt, semi-bron asphalt and blown asphalt; petroleum pitch; coal tar; coal pitch and the like.
When the bituminous substance is blended, the blending amount is preferably 1000 parts by mass or less, more preferably 50 to 500 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). 50 to 200 parts by mass is particularly preferable. Within this range, more stable vibration damping performance (Tan δ) can be imparted over a wide temperature range while maintaining the rubber elasticity of the polyurethane cured product.

As the process oil, for example, (i) a paraffinic process obtained by distillation under reduced pressure of a heavy oil fraction obtained by atmospheric distillation of paraffinic crude oil, and further purifying by hydrogenation reforming, dewaxing treatment, etc. Oil, (ii) naphthenic crude oil after distillation under reduced pressure, solvent extraction, hydrogenation finishing, sulfuric acid washing and clay treatment, (iii) vacuum distillation of paraffinic and naphthenic crude oil Thereafter, an aroma-based process oil obtained as an extract by solvent extraction, and (iv) a plasticizer used for a polyvinyl chloride resin.
Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, Phthalic acid esters such as diundecyl phthalate, ditridecyl phthalate, didodecyl phthalate, diisocumyl phthalate, dinonyl phthalate, alkyl phthalate having 6 to 12 carbon atoms; trioctyl trimellitate, tri-octyl positive decyl trimellitate Trimellitic acids such as diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate Dibutyl diglycol adipate, di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, dimethyl seba Fatty acid esters such as keto, dibutyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinolate, butyl acetyl ricinolate; tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate , Tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl Such as orthophosphoric acid esters such as Le diphenyl phosphate. In addition, chlorinated paraffin, chlorinated fatty acid ester, epoxidized soybean oil, epoxidized linseed oil, epoxy butyl stearate, epoxy octyl stearate, dioctyl terephthalate, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl Examples include glycolate and butylphthalyl butyl glycolate.

  When the process oil is blended, the blending amount is 500 parts by mass or less with respect to a total of 100 parts by mass of the components (A) and (B) from the viewpoint of flexibility, workability, mechanical strength, hardness, and the like. It is preferable that it is 50 to 300 parts by mass, and more preferably 50 to 200 parts by mass.

  Other additives include, for example, stabilizers such as antioxidants, ultraviolet aging inhibitors, antistatic agents, colorants such as pigments and dyes, flame retardants, antibacterial agents, mold release agents such as stearic acid, and rosin derivatives. An adhesive elastomer such as “Rheostomer (registered trademark) B” (manufactured by Riken Technos Co., Ltd.).

The composition of the present invention can be obtained by a known one-shot method or prepolymer method. In preparing the composition, a mixing device or a kneading device is used, and if necessary, in the presence of a solvent having no active hydrogen (for example, ketones, esters, hydrocarbon compounds, etc.), preferably 0 to 0. The mixture is stirred and mixed at 120 ° C., more preferably 15 to 100 ° C., for about 0.5 second to 8 hours, preferably 1 second to 5 hours.
Hereinafter, the preparation method of the composition by the one-shot method and the prepolymer method will be briefly described, but the method is not particularly limited to the following method.

<One-shot method>
Components (A) and (B) and, if necessary, a polyol compound and / or a polyamine compound and the above-mentioned “other components” are mixed, and a polyisocyanate compound and, if necessary, a catalyst are added to the mixture. The composition according to the present invention is obtained and mixed at a predetermined temperature and for a predetermined time, whereby the vibration-damping polyurethane cured product of the present invention can be obtained.
<Prepolymer method>
First, components (A) and (B), a polyol compound and a polyisocyanate compound are reacted to obtain a prepolymer. Subsequently, all the remaining components including the obtained prepolymer and the curing agent are mixed to obtain the composition of the present invention, and the vibration-damaged polyurethane cured product of the present invention is obtained by mixing for a predetermined temperature and for a predetermined time. be able to.

  The polyurethane cured product thus obtained has a maximum value of Tan δ of 1.0 or more, and the maximum value can be adjusted to about 2.0 or even 3 or more by controlling the compounding ratio of the components. Tanδ can be 0.12 or more, more preferably 0.2 or more, and in addition, Tanδ can be 0.1 or more, further 0.2 or more over the range of −40 to 100 ° C. You can also. For this reason, the polyurethane cured product is used as a vibration damping material (referred to as a polyurethane vibration damping material). For example, it is used for the protection of ceilings, inner walls, bridges, roads, and the like of transportation equipment such as automobiles, railway vehicles, and airplanes. Vibration / damping / sound-insulating / absorbing / sound-proofing materials; damping / sound-proofing materials for home appliances / OA equipment; shock absorbers (particularly viscoelastic dampers that absorb shock displacement and vibration of skeletal structure forming materials in the building field) Material); seismic isolation material; used as a vibration isolator for acoustic equipment and precision equipment such as CD players that are extremely sensitive to vibration.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples. In addition, the dynamic viscoelasticity measurement performed in an Example was implemented on condition of the following.
[Dynamic viscoelasticity measurement]
The test was performed in accordance with JIS K7244-4: 1999 dynamic mechanical property test method, Part 4: Tensile vibration-non-resonance method, under the following apparatus and conditions.
Device: “DMS6100 viscoelasticity measuring device”
(EXSTAR6000 series, manufactured by SII Nanotechnology Inc.)
Specimen shape: length 20mm, width 4mm, thickness 2mm
Conditions: Frequency 1 Hz, temperature rising rate 2 ° C./min

<Example 1>
As a component (A), 75 parts by weight of “Krasol LBH-P3000” (component; polybutadiene polyol, number average molecular weight 3000, 1,4 bond ratio 35%, average number of hydroxyl groups in molecule 2.0, manufactured by Sartomer) and component ( B) 25 parts by mass of “Poly bd R-45HT” (component: polybutadiene polyol, number average molecular weight 2,800, 1,4 bond ratio 80%, average number of hydroxyl groups 2.3 in the molecule, manufactured by Idemitsu Kosan Co., Ltd.) , “Millionate MTL” (component; carbodiimidized diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.) as a component (C) with stirring and mixing, and then dibutyltin dilaurate (Manufactured by Kyodo Yakuhin Co., Ltd.) 0.05 parts by mass and 10 MPa in a 2 mm thick mold After curing for 1 hour at beauty 120 ° C., and cured 70 ° C. 15 hours. A test piece (20.0 mm × 4.2 mm × 2.0 mm) was cut out from the cured product thus obtained, and the internal loss (Tan δ) was measured by dynamic viscoelasticity measurement. The results are shown in Table 1 and FIG.

<Example 2>
In Example 1, except that 100 parts by mass of “Diana Process Oil AC-12” (aromatic process oil, manufactured by Idemitsu Kosan Co., Ltd.) was further added to the components (A) to (C) and mixed with stirring. Experiments and measurements were performed in the same manner as in Example 1. The results are shown in Table 1 and FIG.

<Example 3>
In Example 1, Example 1 except that 25 parts by mass of “Clite Mica 200-D” (component; Mica, manufactured by Kuraray Trading Co., Ltd.) was further added to components (A) to (C) and mixed by stirring. Experiments and measurements were performed in the same manner. The results are shown in Table 1.

<Example 4>
In Example 1, 100 parts by mass of “A-80” (component; asphalt, manufactured by Idemitsu Kosan Co., Ltd.) was further added to components (A) to (C), and the mixture was stirred and mixed, as in Example 1. Experiments and measurements were performed. The results are shown in Table 1 and FIG.

<Example 5>
In Example 1, the component (A) was added to 75 parts by mass of “Krasol HLBH-P3000” (component; hydrogenated polybutadiene polyol, number average molecular weight 3000, average number of hydroxyl groups in the molecule 2.0), and the component (B) was changed to “ "Epol" (registered trademark, component; hydrogenated polyisoprene polyol, number average molecular weight 2500, 1,4 bond rate 80%, average number of hydroxyl groups in the molecule 2.3, manufactured by Idemitsu Kosan Co., Ltd.) (C) is changed to “Dismodule W” (component: hydrogenated diphenylmethane diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and further “DS-128” (component: polyalphaolefin, manufactured by INEOS)
Experiments and measurements were performed in the same manner as in Example 1 except that 100 parts by mass was added and stirred and mixed. The results are shown in Table 1.

<Example 6>
In Example 1, experiments and measurements were performed in the same manner as in Example 1 except that the component (A) was changed to 50 parts by mass and the component (B) was changed to 50 parts by mass. The results are shown in Table 1 and FIG.

<Example 7>
In Example 1, experiment and measurement were performed in the same manner as in Example 1 except that component (A) was changed to 25 parts by mass and component (B) was changed to 75 parts by mass. The results are shown in Table 1 and FIG.

<Example 8>
In Example 1, except that 100 parts by mass of “Diana Process Oil NS-90” (naphthenic process oil, manufactured by Idemitsu Kosan Co., Ltd.) was further added to the components (A) to (C) and mixed with stirring. Experiments and measurements were performed in the same manner as in 1. The results are shown in Table 1 and FIG.

<Example 9>
Example 1 is the same as Example 1 except that 100 parts by mass of di-2-ethylhexyl phthalate (DOP) (manufactured by Daihachi Chemical Industry Co., Ltd.) is further added to components (A) to (C) and mixed by stirring. Experiments and measurements were performed in the same manner. The results are shown in Table 1 and FIG.

<Example 10>
In Example 2, experiments and measurements were performed in the same manner as in Example 2 except that the addition amount of “Diana Process Oil AC-12” (aromatic oil, manufactured by Idemitsu Kosan Co., Ltd.) was 50 parts by mass. The results are shown in Table 1 and FIG.

<Example 11>
In Example 2, experiments and measurements were performed in the same manner as in Example 2 except that the addition amount of “Diana Process Oil AC-12” (aromatic oil, manufactured by Idemitsu Kosan Co., Ltd.) was 150 parts by mass. The results are shown in Table 1 and FIG.

<Comparative Example 1>
In Example 1, experiment and measurement were performed in the same manner as in Example 1 except that component (A) was changed to 0 part by mass and component (B) was changed to 100 parts by mass. The results are shown in Table 1 and FIG.

<Comparative example 2>
The experiment was performed in the same manner as in Example 1 except that the component (A) was changed to 100 parts by mass and the component (B) was changed to 0 part by mass. However, the composition remained liquid and a cured product could not be obtained.

<Comparative Example 3>
In Example 5, experiment and measurement were conducted in the same manner as in Example 5 except that the component (A) was changed to 0 part by mass and the component (B) was changed to 100 parts by mass. The results are shown in Table 1.

  From Table 1 and FIGS. 1 to 9, the polyurethane cured product (damping material) of the present invention has a maximum value of Tan δ of 1.0 or more and Tan δ in a wide temperature range from about −40 ° C. to 100 ° C. Is 0.1 or more, and can be said to have stable and high vibration damping performance. In addition, it has excellent vibration damping properties at room temperature (about 23 ° C.) and has high utility value. In particular, the polyurethane cured products obtained in Examples 2, 5, and 8 to 11 were shown to have very high vibration damping performance. On the other hand, from Table 1 and FIG. 10, in the polyurethane cured product obtained by blending only one of the component (A) and the component (B), the maximum value of Tan δ is less than 1.0, and In the range of −40 ° C. to 100 ° C., there is a region where Tan δ is less than 0.1, and stably maintaining high vibration damping performance in a wide temperature range such as the polyurethane cured product of the present invention is could not.

  The polyurethane cured product (damping material) of the present invention is a vibration-proofing / damping / sound-proofing / sound-absorbing / soundproofing material for ceilings and inner walls, bridges, roads, etc. of transportation equipment such as automobiles, railway vehicles and airplanes. ; Vibration control and soundproofing materials for home appliances and OA equipment; Shock absorbers (particularly materials that make up viscoelastic dampers that absorb shock displacement and vibration of skeletal structure forming materials in the building field); Seismic isolation materials; CD players, etc. It can be widely used as an anti-vibration material for acoustic equipment and precision equipment that are extremely sensitive to vibration.

It is a dynamic viscoelasticity measurement result in Example 1. It is a dynamic viscoelasticity measurement result in Example 2. It is a dynamic viscoelasticity measurement result in Example 4. It is a dynamic viscoelasticity measurement result in Example 6. It is a dynamic viscoelasticity measurement result in Example 7. It is a dynamic viscoelasticity measurement result in Example 8. It is a dynamic viscoelasticity measurement result in Example 9. It is a dynamic viscoelasticity measurement result in Example 10. It is a dynamic viscoelasticity measurement result in Example 11. It is a dynamic viscoelasticity measurement result in the comparative example 1.

Claims (9)

  (A) a conjugated diene polymer having a 1,4 bond ratio of 50% or less and having a hydroxyl group at the molecular end; and (B) a conjugated diene polymer having a 1,4 bond ratio of 60% or more and having a hydroxyl group at the molecule end; And (C) a composition containing a polyisocyanate compound.   Furthermore, the composition of Claim 1 containing 0-500 mass parts of process oil with respect to a total of 100 mass parts of the said component (A) and a component (B).   Furthermore, the composition of Claim 1 or 2 containing 0-1000 mass parts of bituminous substances with respect to a total of 100 mass parts of the said component (A) and a component (B).   Furthermore, the composition of any one of Claims 1-3 containing a filler.   The composition according to any one of claims 1 to 4, wherein the conjugated diene-based polymers in the components (A) and (B) are each a polymer composed of butadiene and / or isoprene or a hydrogenated product thereof.   The composition of any one of Claims 1-5 whose compounding ratio of a component (A) and a component (B) is (A) :( B) = 95: 5-5: 95.   The ratio (NCO / OH) of the number of isocyanate groups (NCO) that component (C) has and the total number of hydroxyl groups (OH) of components (A) and (B) is 0.5 to 2.5, Item 7. The composition according to any one of Items 1 to 6.   The polyurethane hardened | cured material obtained by hardening | curing the composition of any one of Claims 1-7.   The polyurethane damping material obtained by hardening | curing the composition of any one of Claims 1-7.

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