WO2008053725A1 - Résine d'uréthane pour des matériaux d'amortissement de vibration et composition pouvant durcir - Google Patents

Résine d'uréthane pour des matériaux d'amortissement de vibration et composition pouvant durcir Download PDF

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Publication number
WO2008053725A1
WO2008053725A1 PCT/JP2007/070479 JP2007070479W WO2008053725A1 WO 2008053725 A1 WO2008053725 A1 WO 2008053725A1 JP 2007070479 W JP2007070479 W JP 2007070479W WO 2008053725 A1 WO2008053725 A1 WO 2008053725A1
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Prior art keywords
polyol
vibration damping
urethane resin
polyester ether
damping material
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PCT/JP2007/070479
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English (en)
Japanese (ja)
Inventor
Yukio Matsumoto
Hisashi Sato
Makito Nakamura
Takeaki Arai
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Asahi Glass Company, Limited
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Publication of WO2008053725A1 publication Critical patent/WO2008053725A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2350/00—Acoustic or vibration damping material

Definitions

  • the present invention relates to a urethane resin for a vibration damping material and a curable composition.
  • a vibration isolator generally prevents vibrations from being transmitted by diffusing vibration energy into the vibration isolator.
  • vibration damping materials can suppress vibrations that propagate through solids, but cannot prevent vibrations that diffuse through the surface of solids.
  • the vibration damping material absorbs vibration by converting vibration energy into heat energy, and even if it is thin, the performance is sufficiently exhibited.
  • 'A method that can be applied to wall materials to prevent the generation of solid-borne sound is considered.
  • the vibration absorption capacity of the damping material is generally expressed by a loss coefficient (tan ⁇ ) expressed by a ratio of loss elastic modulus to storage elastic modulus (loss elastic modulus / storage elastic modulus).
  • Damping materials are often used as bonding layers for adherends such as wall materials and floor materials. did As a result, the damping material is required to have a good adhesive force.
  • the vibration absorption capacity of the entire structure in which the damping material is attached to the adherend is expressed as the product of the storage modulus ratio and loss factor of the adherend and damping material.
  • the material of the adherend such as wall materials and floor materials is storage elasticity compared to resin materials used for vibration damping materials such as wood / fibre materials or stone-concrete materials. A material with a high rate is used. For this reason, in order to increase the vibration absorption capacity of the entire structure with the damping material attached to the adherend, it is preferable to use a material with high V and storage elastic modulus as the damping material.
  • the loss coefficient (tan ⁇ ) expressed by “loss elastic modulus / storage elastic modulus” decreases, so that the balance between the storage elastic modulus and the loss coefficient is improved. I prefer to design.
  • Patent Document 1 describes an acrylic emulsion adhesive as a vibration-damping adhesive that bonds two building boards together!
  • the conventional acrylic emulsion adhesives do not have good elongation, if they are used to bond adherends with different thermal shrinkage rates, the adherends will adhere due to thermal expansion and contraction of the adherends. Stress is concentrated at the interface between the body and the adhesive layer, and peeling easily occurs
  • Patent Document 2 discloses a polyester ether polyol produced by reacting a polyether polyol with a polycarboxylic acid anhydride and a monoepoxide, a chain extender, and a polyisocyanate compound in the presence of an auxiliary agent such as a catalyst.
  • an auxiliary agent such as a catalyst.
  • Polyurethane resins are used in a wide range of applications such as adhesives, coating materials, sealing materials, flooring materials, elastic paving materials, and waterproofing materials due to their excellent adhesion and flexibility.
  • the adhesiveness to polychlorinated bur sheet or aluminum sheet is excellent, and the adipic acid-based polyester polyol has high crystallinity. It tends to become solid at room temperature, and there is a problem in workability. In the one-component moisture-curing type, moisture does not easily penetrate into the resin, and moisture curability tends to be insufficient.
  • phthalate-based polyester polyol has a problem in that it requires a large amount of a solvent and a plasticizer in combination because it has a higher viscosity when it is made into a polymer having a very high viscosity although it has no crystallinity. is there.
  • a method of using a prepolymer using a polyester polyol and a prepolymer using a polyether polyol has also been proposed, but there is a problem of separation due to poor compatibility.
  • Patent Documents 3 and 4 propose a method in which a polyester polyether block copolymer obtained by adding an alkylene oxide to a polyester polyol is used as an adhesive.
  • a polymer composed of a block copolymer chain of a polyester chain and a polyether chain is used, it cannot be sufficiently reduced in viscosity because it easily aggregates.
  • the curable composition used for the adhesive application is excellent in adhesiveness and low in viscosity, it is difficult to achieve both of them. Also obtained great adhesion Therefore, it is preferable that the cured product has good elongation in order to obtain good adhesion durability that preferably has a high breaking strength.
  • Patent Document 1 JP-A-9 203153
  • Patent Document 2 Japanese Patent No. 3097854
  • Patent Document 3 Japanese Translation of Special Publication 2003-511532
  • Patent Document 4 Japanese Patent Laid-Open No. 2004-143314
  • the present invention has been made in view of the above-described problems, and has good adhesiveness, a large loss coefficient and excellent vibration damping properties, and a good balance between elastic modulus and loss coefficient, as well as elongation.
  • An object of the present invention is to provide a two-component curable system for vibration damping materials.
  • Another object of the present invention is to provide a one-part moisture curable composition-forming composition having a low viscosity and excellent adhesiveness, as well as good breaking strength and elongation in a cured product.
  • a polyester polyol is used as a polyuretan resin produced by reacting a conventional polyether polyol (specifically, polyoxyalkylene polyol) with a polyisocyanate compound. Compared to the case, the adhesive strength is inferior. Also
  • tan ⁇ peaks, and in order to adjust the peak to near room temperature, it is necessary to increase the number of functional groups and the number of isocyanates used. Nevertheless, it is difficult to obtain a large tan ⁇ , and the elastic modulus obtained is limited.
  • a polyurethane resin using a polyester polyol and a polyurethane resin using a polyether polyol have better adhesion and easily obtain a high elastic modulus, but since it is crystalline, it has a large tan ⁇ . Can't get.
  • polyester ether polyol (A1) as a component to be reacted with the polyisocyanate compound ( ⁇ )
  • the present inventors have found that a urethane resin for damping material that can solve the conventional problems can be obtained.
  • the present invention has the following gist.
  • a method for producing a urethane resin for a vibration damping material by reacting a polyol (A) with a polyisocyanate compound (B),
  • Polyester ether polyol obtained by copolymerizing the polycarboxylic acid anhydride (b) and the alkylene oxide (c) with the initiator (a) in the presence of the catalyst (X).
  • a method for producing a urethane resin for a vibration damping material comprising (A1).
  • the polyol (A) is a polyester ether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (c) with an initiator ⁇ in the presence of a catalyst (X). ) Containing a urethane resin for vibration damping materials.
  • a urethane resin for damping material by reacting a main component composed of isocyanate group-terminated polymer obtained by reacting polyol (A) with polyisocyanate compound (B) and a curing agent component.
  • Polyester ether polyol obtained by copolymerizing the polycarboxylic acid anhydride (b) and the alkylene oxide (c) with the initiator (a) in the presence of the catalyst (X).
  • a method for producing a urethane resin for a vibration damping material comprising (A1).
  • the polyol (A) contains two or more polyester ether polyols (A1), and the two or more polyester ether polyols (A1) have different glass transition temperatures.
  • the loss coefficient of the urethane resin for vibration damping material is 0.1 or more in the range of 10 to 50 ° C.
  • a urethane prepolymer for a damping material comprising an isocyanate group-terminated polymer obtained by reacting a polyol (A) with a polyisocyanate compound (B),
  • Polyester ether polyol obtained by copolymerizing the polycarboxylic acid anhydride (b) and the alkylene oxide (c) with the initiator (a) in the presence of the catalyst (X).
  • a urethane prepolymer for a vibration damping material comprising (A1).
  • a two-component curable system for a vibration damping material comprising: a main agent composition containing the urethane prepolymer for vibration damping material according to (8) above; and a cured composition containing a hardener component.
  • a one-component moisture-curable composition comprising an isocyanate group-terminated polymer obtained by reacting a polyol (A) having a hydroxyl value of 10 to 300 mgKOH / g and a polyisocyanate compound (B) as a curing component. ,
  • a polyester ether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (c) with respect to the polyol (A) 1S initiator (a).
  • One-part moisture curable composition obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (c) with respect to the polyol (A) 1S initiator (a).
  • a one-component moisture curable composition having a low viscosity and excellent adhesiveness and good breaking strength and elongation in a cured product can be obtained.
  • the initiator (a) used in producing the polyester ether polyol (A1) it is preferable to use a compound having 2 to 8 active hydrogen atoms per molecule.
  • examples include polyhydric alcohols, polyamines, alkanolamines, and phenols.
  • Preferable specific examples include ethylene alcohol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and dihydric alcohols such as 1,4 butanediol; trimethylolpropane, trimethylolethane, and glycerin.
  • Trihydric alcohols Trihydric alcohols; tetrahydric alcohols such as pentaerythritol; hexahydric alcohols such as sorbitol and dipentaerythritol; and polyhydric alcohols such as octahydric alcohols such as sucrose; ethylenediamine, hexamethylenedi And polyamines such as amine and tolylenediamine; alkanolamines such as monoethanolamine, propanolamine, and diethanolamine; and phenols such as bisphenol A.
  • polyoxytetramethylene polyol, polyester polyol, and polycarbonate polyol having a hydroxyl value-based molecular weight per hydroxyl group of 150 to 1500 (hydroxyl value 37 to 374 mg KOH / g) can be used as the initiator ⁇ .
  • polyester polyol include those obtained by condensation reaction of polyhydric alcohols and polycarboxylic acids, and those obtained by ring-opening polymerization of latathone monomers using polyhydric alcohols as initiators. It is done.
  • the initiator ⁇ is preferably a polyhydric alcohol or a polyether polyol having a hydroxyl value-converted molecular weight per hydroxyl group of 150 to 1500 (hydroxyl value 37 to 374 mgKOH / g) to which an alkylene oxide is added using a polyhydric alcohol as an initiator. ! /
  • This polyether polyol is particularly preferred when a double metal cyanide complex catalyst is used as the catalyst (X) in the production of the polyester ether polyol (A1).
  • the hydroxyl value-converted molecular weight of the polyol is a value calculated using the following formula using the hydroxyl value measured by a method based on JIS K1557.
  • Hydroxyl value-converted molecular weight (56100 / hydroxyl value) X number of hydroxyl groups in the polyol.
  • the number of hydroxyl groups of the polyester ether polyol (A1) corresponds to the number of active hydrogen atoms per molecule of the initiator (a). In the present invention, it is more preferable to use a compound having 2 to 3 active hydrogen atoms per molecule as the initiator (a).
  • the number of hydroxyl groups of the polyester ether polyol (A1) in the present invention is preferably 2 to 3 is more preferable.
  • the use ratio of the initiator (a) is preferably from! To 60 mass%, more preferably from 10 to 60 mass%, based on the total amount of all raw materials used in the synthesis of the polyester ether polyol (A1). It is preferable that the proportion of the initiator (a) used is equal to or more than the lower limit of the above range because the initiator characteristics tend to appear. When the proportion of initiator ⁇ used is below the upper limit of the above range, the amount of polycarboxylic acid anhydride in the polyester ether polyol is large, so that the resulting urethane resin (the vibration-damping urethane resin and the polymer are cured by moisture). Excellent in mechanical properties, vibration damping properties and adhesive properties.
  • polycarboxylic acid anhydride (b) in the present invention examples include phthalic anhydride and anhydrous maleic acid.
  • examples include oleic acid and succinic anhydride.
  • aromatic polycarboxylic acid anhydrides are preferred because they have a very high cohesive strength and high polarity and contribute greatly to the adhesion to various adherends. Phthalic anhydride is particularly preferred.
  • the proportion of the polycarboxylic acid anhydride (b) used is preferably 5 to 50% by mass with respect to the total amount of all raw materials used in the synthesis of the polyester ether polyol (A 1). More preferred is 15 to 40% by mass.
  • the use ratio of the polycarboxylic acid anhydride (b) 5% by mass or more the mechanical strength and adhesiveness of the resulting urethane resin can be improved.
  • the glass transition temperature (hereinafter, Tg) of the finally obtained urethane resin for vibration damping material may be abbreviated. ) Can be adjusted to around room temperature.
  • Tg glass transition temperature of the finally obtained urethane resin for vibration damping material
  • the use ratio of the polycarboxylic acid anhydride (b) is 10% by mass or more, the mechanical strength and the adhesiveness are good. Further, when the use ratio is 50% by mass or less, the viscosity of the obtained polyester ether polyol (A1) can be kept low.
  • the alkylene oxide (c) polymerized with the initiator (a) together with the polycarboxylic acid anhydride (b) is preferably an alkylene oxide having 2 to 4 carbon atoms. Specific examples include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and ethylene oxide. Only one type of alkylene oxide may be used, or two or more types may be used in combination. In the present invention, it is particularly preferable to use only propylene oxide, where ethylene oxide or propylene oxide is preferred.
  • the amount of alkylene oxide (c) used is preferably 50/50 to 95/5 in terms of molar ratio (c / b) to polycarboxylic anhydride (b), from 50/50 to 80/20 I like it.
  • molar ratio of anolylene oxide (c) equal to or higher than the lower limit of the above range, it is possible to prevent unreacted polycarboxylic acid anhydride (b) from remaining in the polyester ether polyol (A1).
  • the acid value of the polyester ether polyol (A1) can be lowered.
  • the adhesiveness of the obtained urethane resin, damping property, and mechanical strength are excellent by setting it as below the upper limit of the said range.
  • the polyester ether polyol (Al) in the present invention can be produced by addition polymerization of the polycarboxylic acid anhydride (b) and the alkylene oxide (c) to the initiator (a). Thus, it is preferable to use the catalyst (X) for this polymerization reaction.
  • a ring-opening addition polymerization catalyst is suitably used, and specific examples include alkali catalysts such as potassium hydroxide and cesium hydroxide; double metal cyanide complex catalysts; phosphazene catalysts and the like.
  • the complex metal cyanide complex is preferably a compound in which an organic ligand is coordinated to a zinc hexanocobaltate complex.
  • organic ligands are ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and alcohols such as tert-butyl alcohol!
  • the polyester ether polyol (A1) is preferably obtained by copolymerizing the polycarboxylic acid anhydride (b) and the alkylene oxide (c) with the initiator (a) in the presence of the catalyst (X). .
  • the polyester ether polyol (A1) can be prepared by the following method. First, the initiator (a), the polycarboxylic acid anhydride (b), and the catalyst (X) are charged in advance in a reaction vessel, and the reaction is carried out while slowly adding the alkylene oxide (c). At that time, polycarboxylic acid anhydride (b) has a faster ring-opening reaction than alkylene oxide (c), and polycarboxylic acid anhydride (b) does not undergo a continuous addition reaction. A copolymer having a copolymer chain in which an anhydride (b) and an alkylene oxide (c) are alternately added by 1 mol can be obtained.
  • the acid value of the resulting polyester ether polyol (A1) can be reduced by adding an excess of alkylene oxide (c) and adding only the alkylene oxide (c) to the terminal with a block.
  • the acid value of the polyester ether polyol (A1) is preferably 2. OmgK OH / g or less. 1. OmgKOH / g or less is more preferable. It is preferable that the acid value of the polyester ether polyol (A1) is not more than the above upper limit value because the reactivity with the isocyanate is good and the hydrolysis resistance of the resulting urethane resin is excellent.
  • polyester ether polyol (A1) the portion where the polycarboxylic acid anhydride (b) and the alkylene oxide (c) are alternately added by 1 mole is constant in the ratio of the initiator (a).
  • the overall structure depends on the molecular weight and the amount of terminal alkylene oxide (c) added.
  • the compatibility is insufficient. Even if this mixture is converted into a prepolymer, it is easily separated over time and has insufficient compatibility. In addition, even if a urethane resin is obtained using this prepolymer and a film is formed, a uniform sheet cannot be obtained.
  • the hydroxyl value of the polyester ether polyol (A1) is 11 to 112 mgKOH / g, preferably 22 to 80 mgKOH / g. That is, the molecular weight in terms of hydroxyl value per hydroxyl group is preferably from 500 to 5000, particularly preferably from 700 to 2500. When the molecular weight in terms of hydroxyl value per hydroxyl group is 500 or more, the resulting urethane resin has excellent vibration damping properties and mechanical properties, and excellent adhesion to the adherend substrate. If the molecular weight per hydroxyl group is 5,000 or less, the resulting urethane resin for vibration damping material has excellent mechanical properties and can achieve low viscosity.
  • the molecular weight in terms of hydroxyl value of the polyester ether polyol (A1) is adjusted by appropriately adjusting the number of moles of polycarboxylic acid anhydride (b) and alkylene oxide (c) to be polymerized with respect to the initiator (a). It can be done easily.
  • the polyester ether polyol (Al) is a value obtained by dividing the molecular weight of the initiator ⁇ from the molecular weight in terms of hydroxyl value and dividing the remaining molecular weight by the number of functional groups of the initiator ⁇ (')
  • It is preferably 1S 100-3000, particularly preferably 200-2000.
  • the above-mentioned ⁇ value obtained by dividing the molecular weight converted from the hydroxyl value by the molecular weight of the initiator and dividing the remaining molecular weight by the number of functional groups of the initiator ( ⁇ ′) '' indicates the polycarboxylic acid anhydride (b) and the alkylene oxide ( It means the average molecular weight per copolymer chain formed by the copolymerization of c).
  • the viscosity of the resulting polyester ether polyol (A1) does not become too high, and when the value ( ⁇ ′) force is 00 or more, good adhesiveness is exhibited. That power S.
  • the number of moles of the polycarboxylic acid anhydride (b) and the alkylene oxide (c) to be polymerized with respect to the initiator (a) is appropriately determined as in the adjustment of the molecular weight in terms of hydroxyl value. It can be easily done by adjusting.
  • the viscosity of the prebolimer at 60 ° C is not particularly limited! /, But the application time, power, etc. of the one-part moisture curable composition are preferably less than 20, OOOmPa's, from 1,000 to A range of 15,000 mPa-s is more preferred.
  • the value of the viscosity in this specification is a value (unit: mPa ⁇ s) obtained by measurement under the condition of 60 ° C. with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: RE-80U model).
  • the polyester ether polyol (Al) may be one type or two or more types.
  • Tg glass transition temperatures
  • the first polyester ether polyol (Al l) which is contained in the polyester ether polyol (A1) and has a glass transition temperature of ⁇ 60 ° C. to ⁇ 30 ° C.
  • a urethane resin for damping material having a high tan ⁇ around room temperature can be obtained.
  • the glass transition temperature (Tg) of the polyester ether polyol (Al) is adjusted to the desired temperature by appropriately adjusting the proportion of the polycarboxylic acid anhydride (b) used in preparing the (A1). be able to.
  • polyoxypropylene glycol not containing polycarboxylic acid anhydride (b) has a glass transition temperature (Tg) of about 1700C, whereas polycarboxylic acid anhydride (b) is 10% by mass or more.
  • the glass transition temperature can be adjusted to -60 ° C or higher.
  • the mass ratio (A11 / A12) of the amount used is preferably in the range of 5/95 to 95/5 ⁇ , from 20/80 to 80/20 I like it.
  • the polyol (A) includes the polyester ether polyol (A1).
  • the content of the polyester ether polyol (A1) in the total amount of the polyol (A) is preferably 30% by mass or more, more preferably 50% by mass or more. Most preferably, substantially 100% by weight is the polyether ether polyol (A1).
  • the hydroxyl value of the polyol (A) is preferably 10 to 300 mg KOH / g 1;! To 1 12 mg KOH / g is more preferred 22 to 80 mg KOH / g is particularly preferred. That is, the molecular weight in terms of hydroxyl value per hydroxyl group is preferably from 187 to 5610, more preferably from 500 to 5000 force S, particularly preferably from 700 to 2500.
  • the polyol (A2) other than the polyester ether polyol (A1) contained in the polyol (A) is a compound having 2 to 8 active hydrogen atoms per molecule.
  • initiators polyoxypropylene polyols, polyoxyethylene polyols, polyoxyethylene propylene polyols obtained by ring-opening addition polymerization of alkylene oxides; polyhydric alcohols and polycarboxylic acids Polyester polyol obtained by the condensation reaction of polyester; Polyester / Repoli Taichi / Le; Poly taxitetramethylene poly Ta / Le; Polycarbonate obtained by ring-opening polymerization of a rataton monomer using polyhydric alcohol as an initiator For example, poly talent.
  • the other polyol (A2) is preferably a polyol having 2 to 8 hydroxyl groups, and preferably 2 or 3 polyols. Hydroxyl value of other polyols (A2) (10-300 mgKOH / g preferred ⁇ , 11-; 112 mgKOH / g preferred ⁇ 22-22 mgKOH / g are particularly preferred. Molecular weight 187-5610 preferred, ⁇ 500-5000 preferred, 700-2500 especially preferred.
  • the content of the other polyol (A2) in the total amount of the polyol (A) is preferably 70% by mass or less, and 50% by mass or less may be more preferably zero.
  • Polyisocyanate compound (B) that can be used in the present invention (simply referred to as polyisocyanate (B)
  • aromatic polyisocyanate compounds such as diphenylmethane diisocyanate and 2,6-tolylene diisocyanate; xylylene diisocyanate, metatetramethylxylene diisocyanate
  • Aralkyl polyisocyanate compounds such as sulfonates; Aliphatic polyisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylenediocyanate; isophorone diisocyanate and 4,4, -methylenebis (Cyclohexyl isocyanate) and other alicyclic polyisocyanate compounds; and urethane, burette, allophanate, carpositimide, and isocyanurate modifications obtained from the polyisocyanate compounds.
  • the polyisocyanate compound (B) has excellent reactivity with the polyol (A), and the viscosity of the resulting urethane resin for damping material or the viscosity of the one-part moisture curable composition tends to be low.
  • Aromatic diisocyanates and their modified products are preferred! /, Te, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate, and these modified products are preferred. ,.
  • the polyisocyanate compound (B) may be used alone or in combination of two or more.
  • the isocyanate group-terminated polymer in the present invention is obtained by reacting the polyol (A) with the polyisocyanate compound (B).
  • the isocyanate group-terminated polymer is composed of the polyol (A) and the polyisocyanate compound (B) in a molar ratio of isocyanate group to hydroxyl group (isocyanate group / hydroxyl group). Can be obtained by reacting so that becomes 1 ⁇ 3 ⁇ ; 10.0.
  • the molar ratio is more preferably 1.8 to 7.0.
  • the viscosity of the produced prepolymer does not become too high, which is preferable in terms of workability and moisture curability. Further, if it is 10.0 or less, the mechanical properties of the cured product of the curable composition finally obtained with little remaining unreacted polyisocyanate compound ( ⁇ ) will be improved.
  • the isocyanate group content in the isocyanate group-terminated prepolymer is preferably from 0.5 to 20% by mass. S is preferred;! To 15% by mass is more preferred;! To 12% by mass is particularly preferred. .
  • the isocyanate group content is 0.5% by mass or more, the viscosity becomes high, which is preferable from the viewpoint of workability and moisture curability.
  • it is 20% by mass or less, the mechanical properties of the cured product of the curable composition finally obtained with little remaining unreacted polyisocyanate compound are improved.
  • the one-component moisture-curable composition of the present invention uses an isocyanate group-terminated polymer obtained by reacting a polyol ( ⁇ ) and a polyisocyanate compound ( ⁇ ) as a curing component that hardens by reaction with moisture,
  • the curing component is moisture-cured, for example, cured without using a chain extender or curing agent such as low molecular weight polyols and polyamines.
  • the one-component moisture-curable composition of the present invention is produced under conditions where moisture does not enter, stored in a sealed container, removed from the container at the time of use, applied to a substrate, and exposed to the atmosphere. It can be cured by reacting moisture (humidity) with isocyanate groups in the curing component.
  • the production method of the one-component moisture curable composition of the present invention is not particularly limited. V, but preferably, the above-mentioned essential components and various additives are added as necessary, and the mixture is mixed under reduced pressure or in a nitrogen atmosphere.
  • the composition is preferably kneaded sufficiently using a stirrer or the like and dispersed uniformly.
  • Examples of the additive that is added to the one-component moisture-curable composition of the present invention as needed include the following. (Curing catalyst)
  • a known catalyst that accelerates the urethane reaction or urea reaction can be used.
  • tertiary amine compounds such as triethylamine, dibutyltin dilaurate, dioctyltin maleate, organic acid tin such as 2-ethylethylhexanoate, Organic acid lead etc. are mentioned.
  • plasticizers examples include dioctyl phthalate, dibutyl phthalate, diisonophthal phthalate, dioctyl adipate, diisonoyl adipate, isodecyl succinate, butyl oleate, tricresyl phosphate, propylene glycol adipate polyester, and coconut oil fatty acid ester. Can be mentioned.
  • a solvent may be added to the one-component moisture-curable composition of the present invention.
  • the use of solvents is especially preferred for adhesives for food packaging films!
  • Solvents that can be used include aliphatic hydrocarbons such as isoparaffin and mineral spirits; acetates such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene Amides such as dimethylformamide.
  • the one-component moisture-curable composition of the present invention can be reduced in viscosity by using a specific polyester ether polyol (A1). Therefore, even if a solvent is used, a good viscosity can be obtained with a small amount. It is also possible to use weak solvents (non-aromatic hydrocarbon solvents).
  • a filler can be mix
  • adhesive applications such as adhesives for building materials, coating materials, sealing materials, elastic pavement materials, waterproofing materials, etc.
  • by blending fillers it becomes dripping even on the standing surface, and the coating amount is uniform and stable , Because the adhesiveness is stabilized.
  • Specific examples of the filler include calcium carbonate, titanium oxide, magnesium carbonate, magnesium oxide, magnesium hydroxide, iron oxide, zinc oxide, barium oxide, zinc carbonate, carbon black, silicas, and diatomaceous earth.
  • the amount of filler used is 0 to 60 in the curable composition (100% by mass). A preferred amount is 0 to 50% by weight. By making the amount 60% by mass or less, the adhesive application workability is good.
  • a thixotropic agent an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a flame retardant, and an adhesion imparting agent can be used as necessary.
  • thixotropic agent examples include fine calcium carbonate, Aerosil (manufactured by Nippon Air Koji Co., Ltd.), aliphatic amide, hydrogenated castor oil, and the like.
  • antioxidants examples include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), diphenylamine, phenylenediamine, and triphenyl phosphite.
  • ultraviolet absorbers examples include hindered phenols, benzotriazoles, and hindered amines.
  • inorganic pigments and organic pigments there are inorganic pigments and organic pigments, and examples of inorganic pigments that can be used include titanium dioxide, zinc oxide, ultramarine, bengara, ritbon, lead oxide, cadmium sulfide, cobalt oxide, and aluminum oxide.
  • organic pigments include azo pigments and copper phthalocyanine pigments.
  • antifoaming agent examples include polysiloxane compounds.
  • a black mouth alkyl phosphate, dimethyl 'methyl phosphate, ammonium polyphosphate, neopentyl bromide monopolyether, brominated polyether, bromine' phosphorus compound can be used.
  • the one-component moisture-curable composition of the present invention has a low viscosity as shown in Examples described later, workability is good. Further, the peel strength after adhesion is high and the adhesiveness is excellent, and the breaking strength and elongation in the cured product are good. Moreover, it can be used for bonding to a wide range of materials.
  • metal materials such as aluminum, iron, and copper
  • resin materials such as polyamide, polyethylene terephthalate, nylon, and polypropylene
  • concrete It can be used for a wide range of materials such as sufalt and stone.
  • wood, aluminum, polyamide, polyethylene terephthalate and other resins are preferred, and particularly excellent adhesion to aluminum.
  • the urethane resin for damping material of the present invention is produced using the polyol (A) and the polyisocyanate compound (B).
  • Preferred production methods include the following three methods: First production method: reacting polyol (A) and polyisocyanate compound (B) with a chain extender and / or a curing agent as necessary. A method for producing a urethane resin for damping material. Second production method: Polyisocyanate compound (B) is reacted with polyol (A) to obtain isocyanate-terminated prepolymer, and the prepolymer is moisture-cured by! /, followeded by urethane for vibration damping A method for producing a resin.
  • Third production method The polyol (A) and the polyisocyanate compound (B) are reacted to obtain an isocyanate group-terminated polymer, and the main component and the curing agent component comprising the prepolymer are reacted to dampen the vibration.
  • the polyol (A) and the polyisocyanate are used so that the isocyanate group / hydroxyl group has a molar ratio of 1.2 to 0.7, preferably 1 .;! Nate (B) is reacted with a chain extender and / or a curing agent as necessary to produce a urethane resin (hardened product) for damping material.
  • the one-shot method is a method for producing a polyurethane by simultaneously adding a polyol (A), a polyisocyanate compound (B), and, if necessary, a chain extender and / or a curing agent to a reactor. Can also be used together.
  • polystyrene (co) polymers such as styrene isoprene rubber, acrylic copolymers, ethylene acrylic copolymers, and modified silicone resins. These may be used alone or in combination of two or more.
  • the proportion of the other polymer used is preferably 100 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the total of the polyol (A), the polyisocyanate compound (B), and the other polymer. . Zero is acceptable.
  • a known chain extender and / or curing agent can be used as the chain extender and / or curing agent.
  • a chain extender refers to a relatively low molecular weight compound having two functional groups that can undergo an addition reaction with an isocyanate group
  • a curing agent refers to a functional group that can undergo an addition reaction with an isocyanate group.
  • the chemical structure of the chain extender and / or curing agent is not particularly limited, and specific examples include the following.
  • Chain extenders include diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4 butanediol, 1,6-hexanediol, neopentinole. Examples include glycone, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, and the like. Of these, 1,4 butanediol is particularly preferred, with ethylene glycol, propylene glycol, 1,4 butanediol, and 1,6-hexanediol being preferred.
  • An amine chain extender can also be used as the chain extender.
  • Particularly preferred amine chain extenders include aromatic amines such as various isomers and derivatives of toluene diamine, and methylene dianiline.
  • aromatic amine having a substituent such as 4,4, -methylenebis (2 chloroaniline), 4,4, -methylenebis (3 chloro-2,2, which has a relatively slow addition reaction with an isocyanate group due to an electron or steric effect.
  • the curing agent include polyfunctional polyols such as glycerin, trimethylolpropane, diethanolamine, and triethanolamine, and polyamines.
  • a filler and various additives may be added to the system for reacting the polyol (A) and the polyisocyanate (B) as necessary. Specifically, the polyol (A), a filler selected as necessary and various additives are mixed, and the polyisocyanate (B) is added to the mixture and reacted.
  • fillers the ability to widely use conventionally known fillers such as ordinary calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, bull paste paste range, glass balloon, chloride
  • fillers such as ordinary calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, bull paste paste range, glass balloon, chloride
  • vinylidene resin balloons, acrylonitrile methacrylonitrile resin balloons, and the like examples thereof include vinylidene resin balloons, acrylonitrile methacrylonitrile resin balloons, and the like, which can be used alone or in combination.
  • the blending ratio of the filler is not particularly limited, but is preferably 100 to 500 parts by mass, more preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the polymer component.
  • a plasticizer an adhesion-imparting agent, a tackifier, a stabilizer, a wax, an anti-aging agent, an ultraviolet absorber, a light stabilizer, a thixotropic agent, and a coloring agent are added as necessary to adjust the viscosity and physical properties.
  • Various additives such as additives can be blended.
  • adhesion-imparting agent a silane coupling agent, a carpositimide compound or the like is used, and as a stabilizer, a hindered phenol compound or a triazole compound is used.
  • the colorant include titanium white, carbon black, and bengara.
  • tackifier examples include rosin ester resin, terpene resin, terpene phenol resin, petroleum resin (aliphatic, aromatic, alicyclic, copolymer, coumarone indene resin), alkylphenol resin. And xylene resin.
  • tackifier examples include rosin ester resin, terpene resin, terpene phenol resin, petroleum resin (aliphatic, aromatic, alicyclic, copolymer, coumarone indene resin), alkylphenol resin. And xylene resin.
  • the polyol (A) and the polyisocyanate are adjusted so that the isocyanate group / hydroxyl group has a molar ratio of 1.3 to 5.0, preferably 1.8 to 4.5.
  • (B) and Reaction is performed to obtain isocyanate group-terminated prepolymers.
  • the isocyanate group-terminated prepolymer is cured by reacting with moisture in the atmosphere to obtain a urethane resin (cured product) for vibration damping materials.
  • the vibration-damping material-liquid moisture-curing composition containing the isocyanate group-terminated prepolymer is produced under conditions where moisture does not enter, stored in a sealed container, removed from the container at the time of use, and adhered. It is applied to the base material and exposed to the atmosphere to cure the moisture to produce a urethane resin for damping material.
  • the liquid-damage curable composition for damping material can be used as a coating-type damping adhesive.
  • the isocyanate group-terminated prepolymer when the isocyanate group / hydroxyl group molar ratio is 1.3 or more, the molecular weight of the obtained prepolymer is appropriately reduced and the viscosity is lowered. From the viewpoints of workability and moisture curability. On the other hand, if it is 5.0 or less, the mechanical properties of the urethane resin for damping material that is finally obtained with little residual unreacted polyisocyanate (B) will be good.
  • the isocyanate group-terminated polymer used in the present method preferably has an isocyanate group content of 0.5 to 10% by mass; more preferably! To 7% by mass.
  • the isocyanate group content is 0.5% by mass or more, the storage stability of the prepolymer and the vibration-damping property after moisture curing are excellent, and when it is 10% by mass or less, vibration damping after moisture curing is achieved. Excellent elongation and vibration-damping properties.
  • the liquid-damage curable composition for vibration damping materials contains a polymer other than the isocyanate group-terminated polymer obtained by reacting the polyol (A) and the polyisocyanate (B). Also good. It is preferable to use a polymer having a glass transition temperature different from that of the isocyanate group-terminated prepolymer as the other polymer, and the temperature (peak temperature) at which the tan ⁇ value of the resulting urethane resin for damping material is increased. Can be expanded.
  • the other polymer may be any polymer that does not contain a functional group that reacts with the isocyanate group in the isocyanate group-terminated prepolymer. Specific examples include those similar to the examples of other polymers in the first production method.
  • the amount of the other polymer used is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the total of the isocyanate group-terminated prepolymer and the other polymer. That's right. Zero is acceptable.
  • the filler and various additives can be blended with the damping material-liquid moisture curable composition, if necessary.
  • the isocyanate group-terminated prepolymer is reacted with moisture in the atmosphere and moisture-cured as in the second production method.
  • it can be cured by reacting with a curing agent component as in the third production method.
  • the polyol ( ⁇ ) and the polyisocyanate are adjusted so that the isocyanate group / hydroxyl group has a molar ratio of 1.3 to 5.0, preferably 1.8 to 4.5.
  • (B) By reacting with (B), an isocyanate group-terminated polymer is obtained, and the isocyanate group-terminated prepolymer is used as a main component, and a urethane resin (cured product) for vibration damping is obtained by reacting with the curing agent component.
  • a two-component curable system for a vibration damping material having the main component composition containing the isocyanate group-terminated prepolymer and the curing composition containing the hardener component is manufactured separately.
  • a cured composition is mixed, the mixture is applied to a substrate to be bonded, and cured by heating at room temperature or, if necessary, to cure the urethane resin for a vibration damping material.
  • the two-component curable system can be used as a coating-type vibration-damping adhesive.
  • the main agent composition is preferably produced under conditions where moisture does not enter, stored in a sealed container, and taken out of the container and mixed with the cured composition at the time of use. Further, the curing reaction is preferably carried out under conditions that do not absorb moisture in the atmosphere, such as in a closed container or by circulating an inert gas such as nitrogen.
  • the isocyanate group-terminated prepolymer used in the present method preferably has an isocyanate group content of 0.5 to 10% by mass; more preferably! To 7% by mass.
  • the urethane resin for damping material obtained is excellent in mechanical properties, and when the content is 10% by mass or less, the elongation of the urethane resin for damping material obtained and Excellent vibration control.
  • the curing agent component a known chain extender and / or curing agent can be used, and the same chain extender and / or curing agent as in the first method can be used.
  • a urethane resin for vibration damping material when producing a urethane resin for vibration damping material, it is preferable to use only a chain extender and not a curing agent! /, But a small amount of curing agent as long as thermoplasticity can be maintained. May be used in combination.
  • the amount of the curing agent component used is a range force S in which the molar ratio of (isocyanate group in the main component) / (hydroxyl group in the curing agent) is 0.7 to 2; A range of 1 is more preferable. When the ratio is within this range, the mechanical properties of the urethane resin for vibration damping material obtained are sufficiently improved by crosslinking.
  • the main component composition or the curing agent composition of the two-component curable system contains another polymer other than the isocyanate group-terminated polymer obtained by reacting the polyol (A) and the polyisocyanate (B). Do it! / It is preferable to use a polymer having a glass transition temperature different from that of the isocyanate group-terminated prepolymer as the other polymer, and the temperature (peak temperature) at which the tan ⁇ value of the resulting urethane resin for vibration damping material is increased. Use the force S to expand the range.
  • the other polymer may be any polymer that does not contain a functional group that reacts with the isocyanate group in the isocyanate group-terminated prepolymer. Specific examples include those similar to the examples of other polymers in the first production method.
  • the proportion of the other polymer used is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the total of the isocyanate group-terminated prepolymer and the other polymer. Zero is acceptable.
  • main component composition or the curing agent composition of the two-component curing system may be used as necessary.
  • the filler and various additives can be blended.
  • a urethane resin for damping material having a good damping property such that tan S (loss factor) is 0.1 or more in the range of 10 to 50 ° C.
  • the temperature (peak temperature) range in which the tan ⁇ value of the resulting urethane resin for vibration damping becomes high For example, in a room temperature range of 10 to 50 ° C, tan ⁇ (loss factor) is 0.2 or more, more preferably 0.3 or more. A urethane resin for materials can be obtained.
  • the urethane resin for damping material obtained by the method of the present invention has good adhesiveness and is suitable as a damping adhesive.
  • a damping adhesive for example, gypsum board, plywood, particle board, fiber board, wood wool cement board, flexible board, calcium silicate board, concrete, slate, ALC board, steel plate, etc. Damping performance can be imparted to the building composite board.
  • the urethane resin for vibration damping material is manufactured using the one-component moisture-curable composition or the two-component curable system
  • the composition or system is applied as a coating-type vibration-damping adhesive. Can work and good workability.
  • part means “part by mass” unless otherwise specified.
  • the polyols used as raw materials in the following examples are as follows. Molecular weight is hydroxyl value It is a converted molecular weight.
  • PPG—1000 Polyoxypropylenediol having a hydroxyl value of 112 mgKOH / g and a molecular weight of 1000, produced using propylene glycol as the initiator and using a KOH catalyst.
  • PPG—2000 (abbreviation): Polyoxypropylene diol having a hydroxyl value of 56 mgKOH / g and a molecular weight of 2000 produced using propylene glycol as the initiator and using a KOH catalyst
  • PBA Poly (butylene diol) adipate diol having a hydroxyl value of 56 mgKOH / g and a molecular weight of 2000, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: NIPPOLAN 4010.
  • IP / MPD (abbreviation): Poly (3 methylpentanolenole) isophthalate diol having a hydroxyl value of 56 mgKOH / g and a molecular weight of 2000, manufactured by Kuraray, trade name P-2030.
  • polyester ether diol (A1-1) in which anhydrous phthalic acid and propylene oxide were polymerized at the end of polyoxypropylene diol. (Hydroxyl value: 58.3 mgKOH / g) was obtained. From the measurement result of 1 H-NMR of the polyester ether diol (A 1 1), it was confirmed that the diol (A1-1) has a polymer chain of phthalic anhydride and propylene oxide.
  • Table 1 shows the values obtained by dividing the molecular weight of the initiator excluding the molecular weight by the number of functional groups of the initiator (M '), glass transition temperature, acid value, and viscosity.
  • the viscosity value is a value (unit: mPa ⁇ s) obtained by measuring at 25 ° C using an E-type viscometer by a method according to JIS K1557 (1970 version).
  • Glass transition temperature (Tg) is measured using a differential thermal analyzer (DSC: manufactured by SII, product name: EXSTAR-DS C-6200)-conditions of heating to 5 ° C / min after cooling to 100 ° C Measured with
  • Polyester in the same manner as in Production Example 1 except that the hydroxyl value of the initiator (a) and the amount of each component (a), (b), (c), (x) used were changed as shown in Table 1. Ether diols (Al—2 to 5) were obtained.
  • Viscosity (mPas / 25t;) 4, 500 26, 200 Over 100,000 70, 000 24, 500
  • the polyol (A) and the polyisocyanate compound (B) were reacted to produce isocyanate group-terminated prepolymers (urethane prepolymers for damping materials).
  • the reaction tank After replacing the inside of the reaction tank with nitrogen, the reaction tank was heated to 90 ° C. while stirring the contents at 100 rpm, and maintained at 90 ° C. for 4 hours. Take out a part of the contents after the reaction, measure the content of isocyanate group (hereinafter sometimes abbreviated as NCO), and confirm that the content is less than the theoretically calculated content. After completion, an isocyanate group-terminated urethane prepolymer (P1) was obtained.
  • NCO isocyanate group-terminated urethane prepolymer
  • polyester ether diol (A1-2-4) produced in Production Examples 2 to 4, isocyanate group-terminated prepolymers (urethane prepolymers for vibration damping materials) were produced.
  • Example 1 the type of the polyester ether polyol (A1) and the amount of MDI that is the polyisocyanate compound (B) were changed as shown in Table 2 in the same manner as in Example 1 except that the isocyanate group terminal was changed. Urethane prepolymers (P2-5) were obtained. Table 2 shows the isocyanate group / hydroxyl molar ratio at the time of preparation of the prepolymer and the isocyanate group content in the obtained prepolymer (P1). In the table, the unit of the numbers in the blending column is parts by mass.
  • Example 1 PPG-2000 (glass transition temperature: 70 ° C.) was used as an initiator in Comparative Example 1 instead of the polyester ether diol (A1-1).
  • Comparative Example 2 PBA was used.
  • Comparative Example 3 an acrylic emulsion adhesive (product name: HC-025, manufactured by Cemedine, containing filler) that is commercially available as a coating-type damping material composition is coated on an OPP film.
  • HC-025, manufactured by Cemedine, containing filler an acrylic emulsion adhesive that is commercially available as a coating-type damping material composition is coated on an OPP film.
  • a coating film having a thickness of 100 inches was formed.
  • the coating film was allowed to stand for one week in an environment at a temperature of 20 ° C. and a relative humidity of 60% to evaporate the moisture in the coating film to obtain a cured film.
  • Each film obtained above was cut into a predetermined shape with a dumbbell cutter and peeled off from the OP P film to prepare a test piece.
  • the physical properties shown in Table 3 were measured. That is, the A hardness was measured by a method according to JISK 6253 (1997 edition). Tensile tests are performed according to JIS K7311 (1995 edition), tensile modulus at 100% elongation (100% ⁇ , unit: MPa), tensile modulus at 300% elongation (300% M, unit: MPa), tensile strength (Ts, unit: MPa) and elongation at break (unit:%) were measured. The glass transition temperature was measured. The results are shown in Table 3.
  • a test piece was prepared by peeling off each of the obtained films from the OPP film, and using a dynamic viscoelasticity measurement device (product name: EXSTAR DM S6100, manufactured by SII)
  • the loss factor (tan ⁇ ) was measured at As an evaluation sample, a film cut into a length of 20 mm, a width of 10 mm, and a thickness of 100 m was used.
  • the loss factor was measured at a frequency of 1 Hz from 100 to 120 ° C and evaluated for temperature dependence. Table 3 shows the measurement results at 10 to 50 ° C.
  • the isocyanate group-terminated prepolymers (P1 to P5 and Q1, Q2) obtained in Examples;! -5 and Comparative Examples 1 and 2 and the acrylic emulsion used in Comparative Example 3 were used. Two test pieces each having a wood force were bonded to each other using the respective adhesives. That is, the above prepolymers (P1 to P5 and Ql, Q2) and the acrylic emulsion adhesive were respectively placed on a test piece made of wood in a length X width X thickness of 25 mm X 25 mm. X 1 mm was applied. After application, a 25 mm wide wood test piece was placed and lightly pressed by hand. This was allowed to stand for 1 week in a bath having a temperature of 23 ° C. and a relative humidity of 60% to cure the above-mentioned prepolymer and acrylic emulsion adhesive.
  • the adhesive strength of the sample thus obtained was evaluated by the following shear test.
  • the shear peel strength was measured using a tensile tester (product name: Tensilon VTM-III-200, manufactured by Toyo Baudwin Co., Ltd.) at a tensile speed of 50 mm / min.
  • the measured values of shear peel strength are shown in Table 3 as adhesive strength (unit: N / m 2 ).
  • the loss factor (tan ⁇ ) is considered to have a damping effect of 0.1 or more.
  • the films obtained in Examples 1 to 5 all have a loss factor of 0.1 or more over a wide temperature range of 10 to 50 ° C, exhibit good vibration damping properties, and 25 ° C.
  • the storage elastic modulus of each is 1 X 10 7 Pa or higher, and the balance between elastic modulus and tan ⁇ is good. The elongation at break was also good. Further, the adhesive strength when the specimens made of wood were adhered by the cured products of the prepolymers of Examples 1 to 5 (urethane resin for vibration damping materials) was also good.
  • the film of Comparative Example 1 obtained by reacting the polyether polyol and the polyisocyanate compound had a low loss factor and insufficient vibration damping.
  • the film of Comparative Example 2 obtained by reacting the polyester polyol and the polyisocyanate compound had a low loss factor and poor elongation at break. If the elongation at break of the film is not good, peeling tends to occur when used for bonding adherends having different heat shrinkage rates.
  • Example 11 the polyester ether diol (A1-1) was added to the polyester ether.
  • An isocyanate group-terminal prepolymer was obtained in the same manner as in Example 11 except for changing to terdiol (Al-5).
  • the isocyanate group / hydroxyl group (molar ratio) was 2 ⁇ 50.
  • Viscosity at NCO content of the obtained Isoshianeto group-terminated prepolymer is 4.87 mass 0/0, 60 ° C was 11, 000 (mPa 's) . This was used as a one-part moisture curable composition.
  • Example 11 An additive was added to the isocyanate group-terminated polymer obtained in Example 11 to produce a one-component moisture-curable composition.
  • Example 11 430 g of isocyanate group-terminated polymer obtained in Example 11 was mixed with 50 g of diisononyl phthalate as a plasticizer, 70 g of toluene as a solvent, and heavy calcium carbonate as a filler (manufactured by Shiraishi Kogyo Co., Ltd .: NS-400 or less the same) )) and 50 g of fine synthetic calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd .: Hakuho Hana CCR) are used as a one-part moisture-curable composition.
  • Example 13 The same additive carotenant as in Example 13 and kneaded with 430 g of isocyanate group-terminated polymer obtained in Example 12 was used as a one-part moisture curable composition.
  • Example 11 the amount of polyester ether diol (A1-1) used was changed to 624 g, and the amount of difurmethane diisocyanate was changed to 376 g. Otherwise, the isocyanate group-terminal prepolymer was obtained in the same manner as in Example 11. The isocyanate group / hydroxy group (molar ratio) was 4.83. The obtained isocyanate group-terminated prepolymer had an NCO content of 9.92% by mass and a viscosity at 60 ° C. of 1,800 (mPa ′s).
  • a mixture obtained by adding the same additive as in Example 13 to 430 g of the obtained prepolymer was kneaded and used as a one-component moisture-curable composition.
  • Example 12 the amount of polyester ether diol (A1-5) used was changed to 622 g and the amount of difurmethane diisocyanate was changed to 378 g. Otherwise, the isocyanate group-terminal prepolymer was obtained in the same manner as in Example 12. Isocyanate group / water The acid group (molar ratio) was 4.74. The obtained isocyanate group-terminated prepolymer had an NCO content of 9.90% by mass and a viscosity at 60 ° C. of 6,000 (mPa ′s).
  • a mixture obtained by adding the same additive as in Example 13 to 430 g of the obtained prepolymer was kneaded and used as a one-component moisture-curable composition.
  • a one-component moisture-curable composition was prepared using a polyether polyol having no ester group instead of the polyester ether polyol (A1).
  • Example 11 an isocyanate group was used in the same manner as in Example 11 except that polyoxypropylene diol (PPG-2000) was used instead of the polyester ether diol (A 11) obtained in Production Example 1. Terminal prepolymers were obtained. The isocyanate group / hydroxy group (molar ratio) was 2.557. The obtained isocyanate group-terminated prepolymer had an NCO content of 4.96% by mass and a viscosity at 60 ° C. of 850 (mPa ′s). This was used as a one-component moisture-curable composition.
  • PPG-2000 polyoxypropylene diol
  • a 11 polyester ether diol
  • a one-part moisture curable composition was prepared using adipic acid-based polyester polyol instead of polyester ether polyol (A1).
  • Example 11 an isocyanate group was used in the same manner as in Example 11 except that poly (butylene diol) adipate diol (PBA) was used instead of the polyester ether diol (A 11) obtained in Production Example 1. Terminal prepolymers were obtained. The isocyanate group / hydroxyl group (molar ratio) was 2.57. The obtained isocyanate group-terminated polymer had an NCO content of 4.90% by mass and a viscosity at 60 ° C. of 10,000 (mPa ′s). This was used as a one-part moisture curable composition.
  • PBA poly (butylene diol) adipate diol
  • Terminal prepolymers were obtained.
  • the isocyanate group / hydroxyl group (molar ratio) was 2.57.
  • the obtained isocyanate group-terminated polymer had an NCO content of 4.90% by mass and a viscosity at 60 ° C. of 10,000 (mPa ′s). This was used as
  • polyester ether polyol (A1) In place of the polyester ether polyol (A1), a one-part moisture curable composition was prepared using phthalic polyester polyol V.
  • Example 11 instead of the polyester ether diol (A 1 -1) obtained in Production Example 1, poly (3-methylpentanediol) isophthalatediol (IP / MPD) was used.
  • An isocyanate group-terminal prepolymer was obtained in the same manner as in Example 1 except that it was used.
  • the isocyanate group / hydroxyl group (molar ratio) was 2.557.
  • the obtained isocyanate terminal prepolymer had an NCO content of 4.98% by mass and a viscosity of 25, OOO (mPa's) at 60 ° C. This was used as a one-part moisture curable composition.
  • a one-part moisture curable composition was prepared using a mixture of phthalic polyester polyol and polyether polyol instead of the polyester ether polyol (A1). That is, 379 g of IP / MPD and 378 g of PPG-2000 were charged and mixed in a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and 243 g of diphenylmethane diisocyanate was further charged. The reaction was performed at 80 ° C for 4 hours in an atmosphere. The isocyanate group / hydroxyl group (molar ratio) was 2.57.
  • the one-component moisture-curable composition obtained in the above examples and comparative examples was applied on a biaxially stretched polypropylene film (OPP film) with an applicator to a thickness of 500 mm, 20 ° C, relative humidity It was cured for one week under the condition of 60% and moisture-cured.
  • OPP film biaxially stretched polypropylene film
  • the obtained film was cut into a predetermined shape with a dumbbell cutter and peeled off from the OPP film to prepare a test piece. The following physical properties were measured.
  • Tensile modulus at 100% elongation (100% M, unit MPa), Tensile modulus at 300% elongation (300% M, unit: MPa), tensile strength at break (Ts, unit: MPa), and elongation at break (E , Unit:%) was measured.
  • the physical properties were measured in accordance with JIS-K7311, using a tensile tester as a measuring instrument, dumbbell No. 3 as a test piece, and a tensile speed of 200 mm / min.
  • A1 25mm wide x 100mm long x 4mm thick wood plywood (hereinafter abbreviated as veneer) 25mm x 25mm in a one-part moisture-curing, composition with a thickness of 0.2mm And applied.
  • 25 mm X 25 mm of a 25 mm wide X 100 mm long X 2 mm thick aluminum plate (hereinafter abbreviated as A1) is connected to the other end of the veneer and the other end of A1.
  • A1 was placed so as to face each other across the coated part, and lightly pressed by hand, and further fixed by clamping with a clamping jig. This was cured for one week under conditions of 23 ° C and 50% relative humidity to obtain a test sample.
  • the one-part moisture curable compositions of Examples 11 and 12 have a low viscosity and are easy to use.
  • the films obtained by immediately curing the compositions have excellent elongation and good breaking strength. In addition, it has high shear peel strength and excellent adhesion.
  • Comparative Example 11 comprising a prepolymer prepared using a polyether polyol has a low viscosity and good film elongation. The film has poor breaking strength and adhesiveness.
  • Comparative Examples 12 and 13 composed of prepolymers prepared using a polyester polyol have good adhesiveness but are inferior in elongation and breaking strength of the cured product (film). If the film does not stretch well, peeling tends to occur when it is used to bond adherends having different heat shrinkage rates.
  • Comparative Example 14 In the composition of Comparative Example 14 consisting of a prepolymer prepared using a mixture of polyether polyol and polyester polyol, the liquid separated when allowed to stand, and the film thickness was 500 with a applicator on a biaxially stretched polypropylene film (OPP film). Even when applied to m, a uniform sheet could not be obtained. For this reason, in Comparative Example 14, the film physical properties and the adhesive properties were not evaluated.
  • the urethane resin for vibration damping material of the present invention has good adhesiveness, a large loss factor and excellent vibration damping properties, a good balance between elastic modulus and loss factor, and good elongation.
  • the one-component moisture curable composition of the present invention is suitable for bonding applications, and specifically has good adhesion to a substrate such as an adhesive, a coating material, a sealing material, an elastic pavement material, or a waterproof material. It can be used for required applications! /.

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  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention propose un procédé suivant lequel on peut obtenir une résine d'uréthane pour des matériaux d'amortissement de vibrations, qui présente une bonne propriété adhésive, d'excellentes propriétés d'amortissement de vibrations avec un coefficient de pertes important (tanδ) et un bon équilibre entre le module d'élasticité et le coefficient de pertes, ainsi qu'un bon allongement. On vise également à proposer une composition à un composant qui peut durcir sous l'effet de l'humidité, qui a une faible viscosité et une bonne propriété adhésive, et dont un article durci montre une résistance à la rupture élevée et un bon allongement. L'invention concerne également un procédé de fabrication d'une résine d'uréthane pour des matériaux d'amortissement de vibrations par la réaction d'un polyol (A) avec un composé polyisocyanate (B), qui est caractérisé par le fait que le polyol (A) décrit ci-dessus contient un polyester polyéther polyol (A1) obtenu par copolymérisation d'un anhydride d'acide polycarboxylique (b) avec un oxyde d'alkylène (c) à l'aide d'un amorceur (a) en présence d'un catalyseur (x). L'invention concerne enfin une composition à un composant qui peut durcir sous l'action de l'humidité, et qui comporte comme composant pouvant durcir un prépolymère terminé par isocyanate, obtenu par la réaction d'un polyol (A) ayant un indice d'hydroxyle de 10 à 300 mgKOH/g avec un composé polyisocyanate, caractérisée par le fait que le polyol (A) décrit ci-dessus contient un polyester polyéther polyol (A1) obtenu par la copolymérisation d'un anhydride d'acide carboxylique (b) avec un oxyde d'alkylène (c) à l'aide d'un amorceur (a) en présence d'un catalyseur (x).
PCT/JP2007/070479 2006-10-27 2007-10-19 Résine d'uréthane pour des matériaux d'amortissement de vibration et composition pouvant durcir WO2008053725A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006292433 2006-10-27
JP2006-292433 2006-10-27
JP2006292432 2006-10-27
JP2006-292432 2006-10-27

Publications (1)

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WO2008053725A1 true WO2008053725A1 (fr) 2008-05-08

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TW (1) TW200840830A (fr)
WO (1) WO2008053725A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010189544A (ja) * 2009-02-18 2010-09-02 Arakawa Chem Ind Co Ltd ポリウレタン樹脂、印刷インキ用組成物、コーティング剤組成物及び接着剤組成物
US20210138770A1 (en) * 2017-05-31 2021-05-13 Bando Chemical Industries, Ltd. Surface protective film
CN116333250A (zh) * 2021-12-22 2023-06-27 长华化学科技股份有限公司 聚氨酯软质泡沫塑料、制备方法及其应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990013588A1 (fr) * 1989-05-12 1990-11-15 Asahi Glass Company Ltd. Production d'un polyol d'ester de polyether et de polyurethane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990013588A1 (fr) * 1989-05-12 1990-11-15 Asahi Glass Company Ltd. Production d'un polyol d'ester de polyether et de polyurethane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010189544A (ja) * 2009-02-18 2010-09-02 Arakawa Chem Ind Co Ltd ポリウレタン樹脂、印刷インキ用組成物、コーティング剤組成物及び接着剤組成物
US20210138770A1 (en) * 2017-05-31 2021-05-13 Bando Chemical Industries, Ltd. Surface protective film
CN116333250A (zh) * 2021-12-22 2023-06-27 长华化学科技股份有限公司 聚氨酯软质泡沫塑料、制备方法及其应用

Also Published As

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