WO2016031825A1 - 制振性ウレタン樹脂組成物、制振性ウレタン樹脂成形体および該成形体の形成方法 - Google Patents
制振性ウレタン樹脂組成物、制振性ウレタン樹脂成形体および該成形体の形成方法 Download PDFInfo
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- WO2016031825A1 WO2016031825A1 PCT/JP2015/073889 JP2015073889W WO2016031825A1 WO 2016031825 A1 WO2016031825 A1 WO 2016031825A1 JP 2015073889 W JP2015073889 W JP 2015073889W WO 2016031825 A1 WO2016031825 A1 WO 2016031825A1
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
- C09K21/04—Inorganic materials containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/10—Organic materials containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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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
- C08G2350/00—Acoustic or vibration damping material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/72—Fillers; Inorganic pigments; Reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
- F16F15/04—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
- F16F15/04—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means
- F16F15/08—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means with rubber springs ; with springs made of rubber and metal
Definitions
- the present invention relates to a vibration-damping urethane resin composition, a vibration-damping urethane resin molded body, and a method for forming the molded body.
- Patent Document 1 describes a material containing an acrylic urethane resin.
- Patent Document 2 describes a resin composition containing particles capable of absorbing, reducing, and suppressing vibration energy, and a binder resin, and core-shell particles having a shell made of a crosslinked resin as the particles. Is described.
- the conventional vibration damping material is inferior in resistance to mechanical stress such as wear and impact, and causes plastic deformation due to heat, A large load such as the lower part of a ship engine is applied, and it is not suitable for a place used in a high temperature atmosphere.
- a molded body obtained from a vibration-damping resin composition containing a microcapsule having an outer shell formed of an organic resin or a porous body formed of an organic resin has a very strong structure of the outer shell resin. Therefore, there is a problem that it is difficult to deform and it is difficult to convert vibration energy into heat energy.
- This invention is made
- phase change substance is at least one selected from paraffin, wax, fatty acid, and polyalkylene glycol.
- phase change material has a melting point of ⁇ 30 to 200 ° C.
- a vibration-damping urethane resin molded product that satisfies the following requirements (1) and (2).
- the loss coefficient (tan ⁇ ) at 80 ° C. and 1 Hz is 0.4 or more.
- the creep change rate when a 4.5 MPa load is applied for one week at 70 ° C. [25] The vibration-damping urethane resin molded product according to [13], which satisfies the requirement of (3).
- Flammability meets UL94 HB standard
- a method for forming a vibration-damping urethane resin molded body including a step of forming the molded body by pouring the vibration-damping urethane resin composition according to any one of [1] to [11] into a construction site.
- a vibration-damping urethane resin composition capable of easily forming a molded article having excellent creep resistance and a large loss factor.
- the molded body formed from such a resin composition has a high vibration damping effect, excellent resistance to compression load and impact resistance, and little plastic deformation due to heat. It can be suitably used even under severe conditions such as in an atmosphere.
- a vibration-damping urethane resin composition exhibiting high fluidity can be obtained even in a solvent-free system
- a molded body can be formed by a method such as pouring.
- a molded body having the above-described effect can be formed in a desired place (even a slight gap for fixing devices).
- the composition of the present invention has the above-mentioned effects, in order to fix devices and the like, a high load, in order to fix devices in a high-temperature atmosphere, and further, vibration damping is required, a high load, It can be suitably used as a composition for forming a molded body for fixing a device under a high temperature atmosphere, for example, a lower part of a ship engine.
- composition of the present invention containing a flame retardant, a molded article having excellent creep resistance and a large loss factor can be obtained.
- the vibration-damping urethane resin composition of the present invention contains inorganic particles (C) encapsulating castor oil-based polyol (A), isocyanate (B), and phase change material. And as needed, you may contain an inorganic pigment (D), a flame retardant (E), and an additive (F) in the range which does not impair the effect of this invention.
- Castor oil is a pale yellow, viscous, non-drying oil obtained from the seeds of a plant called Euglena. Castor oil has about 90% of the fatty acid is ricinoleic acid and has hydroxyl group, double bond and ester bond in one molecule, and therefore has unique characteristics different from other vegetable oils. Its features include excellent stability, flexibility, electrical insulation, water resistance, impact resistance, and the like.
- the composition of the present invention contains a castor oil-based polyol using a castor oil having such characteristics as a starting material, in addition to resistance to mechanical stress such as friction and impact, heat resistance, hydrolysis resistance, A molded article having excellent acid resistance can be formed. In addition, by using the castor oil-based polyol (A), it is possible to form a molded body that hardly undergoes thermal deformation or curing shrinkage.
- polyether polyols or polyester polyols may be used.
- the resulting molded product tends to be too flexible to exhibit desired creep resistance, and when a polyester polyol is used. Therefore, the obtained molded product was too hard and the desired vibration damping property did not appear.
- plays the said effect can be obtained by using a castor oil-type polyol (A).
- the castor oil-based polyol (A) is not particularly limited.
- an ester of castor oil and at least one of alkylene oxide adducts of castor oil and at least one of alcohol, polyester polyol and polyether polyol is used.
- An exchange compound an ester compound of castor oil fatty acid (a fatty acid obtained from castor oil, usually a mixture of ricinoleic acid and oleic acid, etc.) and at least one of alcohol, polyester polyol and polyether polyol; Castor oil diol-type partially dehydrated or partially acylated product; transesterified product, ester compound and hydrogenated product of each of the partially dehydrated product or partially acylated compound; castor oil polymerized to obtain polymerized castor oil Obtained Compounds obtained by reacting the transesterification reaction products and caprolactone polymerization castor oil and the like.
- castor oil type polyol (A) what was synthesize
- Commercially available products include URIC H-102, URIC H-92, URIC H-81, URIC H-73X, URIC H-62, URIC H-420, URIC H-854, URIC H-870, URIC H-1824, URIC AC-006, URIC Y-406, URIC HF-2009 (above, manufactured by Ito Oil Co., Ltd.), HS CM-075P, HS PPE-12H, HS 3P-255, HS 3G-500B, HS 2B-5500, HS 2G-120, TLM, HS CM (manufactured by Toyokuni Oil Co., Ltd.) and the like.
- the castor oil-based polyol (A) is not particularly limited, and examples thereof include a polyol having a hydroxyl value of 30 to 400 mgKOH / g and a functional group number of 1 to 6.
- the castor oil-based polyol (A) is preferably a polyol having a hydroxyl value of 300 mgKOH / g or more and a functional group number of 3 or more, more preferably a polyol having a hydroxyl value of 340 mgKOH / g or more and a functional group number of 3 or more.
- the upper limit of the hydroxyl value may be 400 mgKOH / g, and the upper limit of the number of functional groups may be 6.
- a castor oil-based polyol (A) having a hydroxyl value and the number of functional groups within the above ranges it is possible to obtain a molded article having a well-balanced vibration damping property and creep resistance, and further, the crosslinking density is increased and the strength is increased. In addition, a molded article having excellent heat resistance and a low creep change rate can be obtained. Further, by using a castor oil-based polyol (A) having a hydroxyl value and the number of functional groups within the above ranges, a molded product having a high loss factor can be obtained even at high temperatures.
- the said functional group number represents the number of the hydroxyl groups in a castor oil type polyol (A) 1 molecule.
- Castor oil-based polyols (A) having a hydroxyl value of 300 mgKOH / g or more and a functional group number of 3 or more are specifically URICRH-102, URIC H-92, URIC H-81 (manufactured by Ito Oil Co., Ltd.) Is mentioned.
- the viscosity measured at 25 ° C. using an Ubbelohde viscometer in accordance with JIS Z8803 is preferably 8,000 mPa ⁇ s or less, more preferably 6,000 mPa ⁇ s or less, In particular, it is preferably 3,000 mPa ⁇ s or less.
- the lower limit of the viscosity of the castor oil-based polyol (A) is preferably 30 mPa ⁇ s, more preferably 300 mPa ⁇ s.
- the number average molecular weight (Mn) of the castor oil-based polyol (A) is preferably 4,000 or less, more preferably 2,500 or less, and particularly preferably 2,000 or less.
- the lower limit of Mn of the castor oil-based polyol (A) is preferably 200, more preferably 300.
- the Mn can be calculated and calculated based on the hydroxyl value of the castor oil-based polyol (A). In general, the castor oil-based polyol (A) tends to increase in viscosity as Mn increases.
- the content of the castor oil-based polyol (A) is preferably 25 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 35 to 60% by mass with respect to the total amount of the composition of the present invention. It is. When the content of the castor oil-based polyol (A) is in the above range, a molded article having excellent creep resistance and vibration damping effect can be obtained.
- the castor oil-based polyol (A) may be used alone or in combination of two or more.
- the isocyanate (B) may be a compound that reacts with the castor oil-based polyol (A) and can be cured.
- isocyanate (B) diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) [Example: 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, polymeric MDI (crude MDI) )])), Tolylene diisocyanate (hereinafter abbreviated as “TDI” [Example: 2,4-TDI, 2,6-TDI]), aromatic polyisocyanates such as naphthalene diisocyanate, hexamethylene diisocyanate, isophorone Examples thereof include aliphatic polyisocyanates such as diisocyanate and xylylene diisocyanate, carbodiimide-modified products of the polyisocyanate, and polyurethane prepolymers obtained by reacting
- MDI diphenylme
- carbodiimide-modified isocyanate and / or TDI as the isocyanate (B) from the viewpoint of obtaining a molded article having excellent mechanical strength and creep resistance.
- the carbodiimide-modified isocyanate is preferably carbodiimide-modified MDI.
- carbodiimide-modified MDI and TDI have a flexible segment while having a strong benzene ring as a structure, by using these compounds, they have flexibility while being tough, creep resistance, A molded article having excellent heat resistance can be obtained.
- a commercial item may contain the said isocyanate as a main component, and also may contain the isomer of this isocyanate, etc., or a solvent, In this invention, these commercial items can be used without a restriction
- a solvent-free isocyanate is preferable in that it can form a molded article that is excellent in mechanical strength and creep resistance and hardly undergoes thermal deformation or curing shrinkage.
- Examples of commercially available carbodiimide-modified MDI include Millionate® MTL (manufactured by Nippon Polyurethane Industry Co., Ltd.) and Luplanate® MM-103 (manufactured by BASF® INOAC® Polyurethane Co., Ltd.), and TDI as Cosmonate® T-80 (Mitsui Chemicals, Inc.). And Lupranate® T-80 (BASF® INOAC® Polyurethane Co., Ltd.).
- the inorganic particles (C) encapsulating the phase change material are not particularly limited as long as they are particles enclosing the phase change material inside the inorganic particles.
- the inorganic particles (C) encapsulate the phase change material and are inorganic. Examples include microcapsules having an outer shell formed of a substance, and particles in which a phase change substance is filled in pores of a porous particle formed of an inorganic substance. That is, the inorganic particles (C) include not only the case where the phase change material is completely covered by the outer shell of the inorganic material, but also the inside of the pores of the porous particles formed of the inorganic material.
- the inorganic particles (C) it is possible to obtain a molded body that is easily deformed by a load and that easily converts vibration energy into heat energy. For this reason, this molded object is excellent in a damping effect, creep resistance, heat resistance, etc.
- a microcapsule having an outer shell made of an organic resin such as a melamine resin, an acrylic resin, or a urethane resin may be used.
- an organic resin such as a melamine resin, an acrylic resin, or a urethane resin
- plays the said effect can be obtained by using the said inorganic particle (C).
- the composition of the present invention is different from the composition obtained by adding inorganic particles having pores and a phase change material.
- the phase change material tends to be difficult to uniformly disperse in the urethane resin composition, and the phase change material is bleeded from the obtained molded product.
- the desired vibration damping property does not appear.
- the inorganic particles (C) can be used to uniformly disperse the particles (phase change material) in the urethane resin composition. Conceivable.
- the heat-resistant temperature thereof is sufficiently higher than the melting point of the phase change substance, and can be used for the composition of the present invention.
- a substance having a suitable strength is preferable, and inorganic particles having pores such as silica, calcium carbonate and talc are more preferable.
- the porous particles include particles made of an inorganic substance having pores penetrating from the surface to the inside thereof, and may be hollow particles having cavities inside or particles having no cavities. It may be.
- phase change substance a substance having a melting point between ⁇ 30 to 200 ° C., preferably 0 to 40 ° C. is desirable.
- phase change substance include paraffins such as paraffinic hydrocarbons, waxes such as natural wax and petroleum wax, fatty acids such as capric acid and lauric acid, polyalkylene glycols such as polyethylene glycol, and barium hydroxide octahydrate.
- paraffins such as paraffinic hydrocarbons, waxes such as natural wax and petroleum wax, fatty acids such as capric acid and lauric acid, polyalkylene glycols such as polyethylene glycol, and barium hydroxide octahydrate.
- the phase change substance is preferably at least one selected from paraffin, wax, fatty acid, and polyalkylene glycol.
- a material that causes a solid-liquid phase transition near room temperature that is, a paraffinic hydrocarbon having a melting point of 0 to 40 ° C. is preferably used.
- Specific examples include pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and Examples include Ikosan.
- the phase change substance included in the inorganic particles may be one kind alone, or two or more kinds.
- the inorganic particles (C) may contain a substance other than the phase change substance.
- a substance other than the phase change substance examples include a trapping substance that stably holds the phase change substance in the pores.
- the average particle diameter of the inorganic particles (C) measured with a scanning electron microscope (SEM) is not particularly limited, but from the standpoint of obtaining a molded article having excellent creep resistance and a large loss factor.
- the thickness is preferably 0.5 to 200 ⁇ m, more preferably 1 to 150 ⁇ m.
- C Commercially available inorganic particles (C) include Riken Resins LA-5-100, LA-15-100 and LA-25-100 (manufactured by Miki Riken Kogyo Co., Ltd.).
- the content of the inorganic particles (C) is preferably in the range of 1 to 25% by mass with respect to the total amount of the composition of the present invention.
- the content of the inorganic particles (C) is preferably 6 to 25% by mass.
- the creep resistance is excellent and the loss coefficient tan ⁇ is 0.00.
- a molded body having 5 or more can be easily obtained.
- the obtained molded product tends to be brittle, and when the content is less than 1% by mass, a molded product with excellent vibration damping properties tends not to be obtained. is there. Only 1 type may be used for an inorganic particle (C), and 2 or more types may be used for it.
- the composition of the present invention may contain an inorganic pigment (D) in order to improve resistance to creep change.
- the inorganic pigment (D) is an inorganic substance other than the inorganic particles (C). Only 1 type may be used for an inorganic pigment (D), and it is also possible to use 2 or more types.
- Examples of the inorganic pigment (D) include general constitutions such as silica, talc, mica, potassium feldspar, wollastonite, kaolin, clay, bentonite, titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate, and barium sulfate. Mention may be made of pigments.
- TK-1 silicon, manufactured by Tono Koji Co., Ltd.
- R-5N titanium dioxide, manufactured by Sakai Chemical Industry Co., Ltd.
- Super SS calcium carbonate, China Mining Co., Ltd.
- TTK Talc Talc, Takehara Chemical Industry Co., Ltd.
- Mica Powder 200 Mesh Fukuoka Talc Industrial Co., Ltd.
- NYGLOS 4W Willastonite, NYCO MINERALS, Sakai INC.
- the particle diameter of the inorganic pigment (D) measured in accordance with JIS K 5101 Pigment Test Method Part 14 Sieve Residue is not particularly limited, but is preferably from the viewpoint of obtaining a molded article having excellent creep resistance. It is 1,000 micrometers or less, More preferably, it is 500 micrometers or less.
- the content of the inorganic pigment (D) is preferably 0 to 30% by mass with respect to the total amount of the composition of the present invention, and 5 to 25% by mass from the viewpoint of improving the creep resistance of the molded article obtained. It is more preferable that When it contains more than 30 mass%, it exists in the tendency for the damping property of the molded object obtained to fall.
- the total content of the said inorganic particle (C) and an inorganic pigment (D) is obtained molding. From the standpoint of improving the creep resistance of the body, it is preferably 1 to 55% by mass, more preferably 5 to 50% by mass, based on the total amount of the composition of the present invention.
- the inorganic pigment (D) it is particularly preferable to use silica, and when blended in the range of 12 to 25% by mass with respect to the total amount of the composition of the present invention, the loss factor of the vibration-damping urethane resin molded product
- the tan ⁇ is 0.6 or more, and the creep resistance can be improved without impairing the loss factor.
- the composition of the present invention may contain a flame retardant (E) in order to improve flame retardancy. Only 1 type may be used for a flame retardant (E), and 2 or more types may be used for it.
- Examples of the flame retardant (E) include inorganic, halogen, phosphorus, melamine, and silicone flame retardants.
- the halogen-based flame retardant containing at least one element selected from bromine element and chlorine element exhibits an excellent flame retardant effect.
- a halogen-based flame retardant is used and the molded product obtained from the composition of the present invention burns, a toxic gas may be generated during the combustion. Therefore, it is preferable to use a non-halogen flame retardant as the flame retardant (E).
- some flame retardants have different states such as powder and liquid.
- a liquid flame retardant is added to the composition, the mechanical strength of the molded product obtained from the composition is reduced or bleed-out (bleeding out). ) May occur.
- powdered flame retardants are also added to the composition in large quantities, the original physical properties of the molded product may be impaired. Therefore, as the flame retardant (E), it is preferable to use a powdery flame retardant that exhibits a flame retardant effect in a small amount.
- the flame retardant (E) it is particularly preferable to use a non-halogen flame retardant such as a phosphorus flame retardant or a melamine flame retardant.
- Phosphorus flame retardants include ammonium polyphosphate, phosphate ester, phosphazene, red phosphorus, triphenyl phosphate (TPP), triallyl phosphate, triethyl phosphate, tricresyl phosphate (TCP), cresyl phenyl phosphate, intomesent And flame retardants.
- Melamine flame retardants include melamine, melamine cyanurate, melamine phosphate and the like.
- Intomesent flame retardant which is one of the phosphorus flame retardants
- the flame retardant (E) in the molded body foams.
- a foam-like thermal expansion layer is formed on the surface of the molded body.
- E flame retardant
- Exolit AP422, Exolit AP423, Exolit AP462, Exolit AP750, Exolit AP760 manufactured by CLARIANT
- PHOSMEL200 Nesan Chemical Industry Co., Ltd.
- ADK STAB 2100JC ⁇
- ADK STAB 2200S ⁇
- MC-4000 manufactured by Nissan Chemical Industries, Ltd.
- the content of the flame retardant (E) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and particularly preferably 5 to 15% by mass with respect to the total amount of the composition of the present invention. .
- the content of the flame retardant (E) is within the above range, it is possible to obtain a molded article having excellent flame resistance while having excellent creep resistance and a large loss factor.
- composition of the present invention may further contain an additive (F) other than the above (A) to (E).
- additive (F) include an antifoaming agent, a moisture adsorbent, a catalyst, and other materials. Only 1 type may be used for an additive (F), and 2 or more types may be used for it.
- ⁇ Antifoaming agent> From the viewpoint of obtaining a molded article having excellent creep resistance, it is preferable that no bubbles are present in the molded article. For this reason, it is preferable to mix
- the antifoaming agent include a silicone-based antifoaming agent and a mineral oil-based antifoaming agent, and there are water-based, solvent-based and solvent-free systems, respectively.
- a solvent-free silicone-based antifoaming agent is preferable in order to suppress shrinkage when forming a molded body, and this antifoaming agent is contained in the range of 0 to 3% by mass with respect to the total amount of the composition of the present invention.
- Examples of the commercially available solvent-free silicone-based antifoaming agent include Dow Corning Toray SAG-47 (manufactured by Dow Corning Toray). Only one type of antifoaming agent may be used, or two or more types may be used.
- ⁇ Moisture adsorbent> When forming a molded product from the composition that incorporates moisture that can be contained in inorganic particles (C) and inorganic pigments (D) in the atmosphere, the isocyanate, which is a curing agent, reacts with moisture and can foam. There is sex. In order to suppress this foaming, it is preferable to remove moisture in the system, and for this reason, it is preferable to add a moisture adsorbent to the composition of the present invention.
- the moisture adsorbent is preferably blended in the range of 0 to 10% by mass with respect to the total amount of the composition of the present invention. Only one type of moisture adsorbent may be used, or two or more types may be used.
- the moisture adsorbent is not particularly limited as long as it has moisture adsorption ability, and a conventionally known substance can be used.
- a commercial product of the moisture adsorbent for example, molecular sieve 4A powder (manufactured by Union Showa Co., Ltd.) can be mentioned.
- the composition of this invention may contain the catalyst which accelerates
- catalysts include tin carboxylates, amine catalysts, metal carboxylates other than tin, and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) salts.
- tin carboxylates include dibutyltin dilaurate, dibutyltin diacetate, and tin octylate.
- amine-based catalysts include triethylamine, triethylenediamine, and tetramethylbutanediamine, and examples of metal carboxylates other than tin.
- Examples include cobalt octylate, manganese octylate and zinc octylate, and DBU salts include DBU-stearate, DBU-oleate and DBU-formate.
- GREC TL manufactured by DIC Corporation
- DABCO 33-LV manufactured by Air Products Japan
- Neostan U-28 manufactured by Nitto Kasei Co., Ltd.
- triethylamine Manufactured by Daicel
- the catalyst is preferably contained in the range of 0 to 3% by mass with respect to the total amount of the composition of the present invention. Only 1 type may be used for a catalyst and 2 or more types may be used for it.
- composition of the present invention can further contain a wetting and dispersing agent, a surface conditioner, a rheology control agent, a leveling agent, a plasticizer, a solvent, and the like, as necessary, as long as the object of the present invention is not impaired.
- a wetting and dispersing agent e.g., a surface conditioner, a rheology control agent, a leveling agent, a plasticizer, a solvent, and the like.
- the composition of the present invention does not contain a solvent from the viewpoint that it can form a molded article that hardly undergoes shrinkage due to curing, but depending on the application to be used, in order to obtain a composition with higher fluidity, etc.
- a solvent may be used.
- the viscosity of the composition of the present invention measured at 23 ° C. using a BM viscometer is preferably 40,000 mPa ⁇ s or less, more preferably 30,000 mPa ⁇ s or less.
- a composition having such a viscosity exhibits high fluidity, and it is easy to form a molded body by a method such as pouring.
- the composition of the present invention can be prepared by mixing the components (A) to (C) and, if necessary, the components (D) to (F).
- the composition of the present invention is preferably a two-component type comprising a main agent containing the component (A) and a curing agent containing the component (B) from the viewpoint of storage stability.
- the inorganic particles (C) may be blended in either the main agent or the curing agent, but are preferably blended in the main agent.
- the inorganic pigment (D), the flame retardant (E) and the additive (F) may be blended in either the main agent or the curing agent, but the inorganic pigment (D) and the flame retardant (E) are the main agent. It is preferable to blend in. Moreover, it is preferable to mix
- the composition of the present invention can be prepared by mixing the main agent and the curing agent.
- the vibration-damping urethane resin molded article of the present invention (hereinafter also referred to as “the molded article of the present invention”) is formed from the composition of the present invention. For this reason, the molded body of the present invention has a high vibration damping effect, is excellent in resistance to compression load and impact resistance, and has little plastic deformation due to heat.
- the molded object of this invention satisfy
- the loss coefficient (tan ⁇ ) at 80 ° C. and 1 Hz is 0.4 or more.
- the creep change rate when a 4.5 MPa load is applied for one week at 70 ° C. is 25% or less.
- the molded body of the present invention satisfies the following requirement (3).
- the loss coefficient is the ratio of the storage shear modulus (G ′) to the loss shear modulus (G ′′), G ′′ / G ′, and is expressed by tan ⁇ .
- tan ⁇ When the molded article of the present invention is deformed, It is an index showing how much vibration energy is changed to thermal energy. A larger value of tan ⁇ means that vibration energy is converted into heat energy, that is, there is a vibration damping effect.
- tan ⁇ at 80 ° C. and 1 Hz is preferably 0.4 or more, more preferably 0.5 or more, and 0.6 or more. Is particularly preferred.
- the loss factor can be measured by the method described in the Examples below.
- Resin-based materials may be plastically deformed when a large load is continuously applied for a long time in a high-temperature atmosphere, which is called creep change.
- the creep change rate when a load of 4.5 MPa is applied for 1 week under an atmosphere of 70 ° C. is preferably as small as possible, preferably 25% or less, and more preferably less than 20%. If the creep change rate exceeds 25%, the molded body may be broken or cracked due to deformation.
- the creep change rate can be measured by the method described in the examples below.
- the molded body having the loss factor and the creep change rate can be easily formed by using the composition of the present invention.
- the most common flammability certification standard for plastic materials is the UL94 standard (a US combustion test standard established by Underwriters Laboratories Inc.).
- the combustibility of the molded product of the present invention can be evaluated using an HB (horizontal combustion) test, which is a method for evaluating a solid plastic material, and the molded product preferably satisfies the HB standard.
- HB horizontal combustion
- the flammability can be measured by the method described in the following examples.
- the molded body having flame retardancy can be formed by using, for example, a composition containing a flame retardant (E).
- the molded article of the present invention can be formed by casting, extrusion molding, injection molding, RIM molding using the composition of the present invention. And it can form by apply
- the substrate include concrete, mortar, slate plate, plywood, tile, metal, glass, film, fiber and the like, and these substrates may be subjected to surface treatment.
- the composition of the present invention is formed by directly pouring the composition into a place (construction site) where the molded article of the present invention is to be formed and curing the composition. Is preferred. This method is preferable because the compact can be sufficiently filled into a narrow gap.
- the molded body of the present invention can be suitably used for vibration generating objects such as ships, automobiles, railways, airplanes, buildings, industrial equipment, home appliances and precision equipment, among which high temperatures such as those around the engine are particularly high. Suitable for use in an atmosphere.
- the molded article of the present invention is particularly suitable for use in the lower part of a marine engine, and in the case of a marine engine equipped with a main engine and an auxiliary engine, it can be suitably used in the lower part of the auxiliary engine.
- the molded article of the present invention is excellent in vibration damping properties, so that the auxiliary machine engine can be protected from vibration caused by the main engine when the auxiliary machine engine is not operating.
- Example 1 80.0 parts of castor oil-based polyol URIC H-102 (manufactured by Ito Oil Co., Ltd.) and 20.0 parts of Riken Resin LA-15-100 (manufactured by Miki Riken Kogyo Co., Ltd.) are charged into a container, and the outer shell of the microcapsule is Dispersion was performed for 10 minutes at 500 rpm or less using a high-speed disper so as not to break.
- the urethane resin composition after defoaming was poured into a 100 ⁇ 100 ⁇ 25 mm molding frame, cured at 23 ° C. for 16 hours, and cured to prepare a urethane resin molded body.
- Examples 2 to 17, Comparative Examples 1 to 7 A urethane resin composition was prepared in the same manner as in Example 1 except that the types and amounts used of the raw materials were changed as shown in Table 2 or 4, and the same as in Example 1 except that the resulting composition was used. Thus, a urethane resin molded body was prepared. The details of each material in Table 2 or 4 are as shown in Table 1.
- Example 18 80.0 parts of castor oil-based polyol URIC H-81 (manufactured by Ito Oil Co., Ltd.) and Exolit AP462 (manufactured by CLARIANT) were charged into a 15.0 part container, and dispersed at 1000 rpm for 15 minutes using a high speed disper. Thereafter, 20.0 parts of Riken Resin LA-15-100 (manufactured by Miki Riken Kogyo Co., Ltd.) was blended, and dispersed for 10 minutes at 500 rpm or less using a high-speed disperser so as not to destroy the outer shell of the microcapsule. .
- the urethane resin composition after defoaming was poured into a 100 ⁇ 100 ⁇ 25 mm molding frame, cured at 23 ° C. for 16 hours, and cured to prepare a urethane resin molded body.
- Example 19 to 25 Except having changed the kind and usage-amount of a raw material as shown in Table 3, it prepared similarly to Example 18 and prepared the urethane resin composition, and it was carried out similarly to Example 18 except having used the obtained composition. A urethane resin molded body was prepared. The details of each material in Table 3 are as shown in Table 1.
- the thickness of the specimen was measured before the load was applied and one week after the load was applied, and the rate of change in the thickness direction of the specimen before and after the load was calculated.
- the rate of change was measured in the same manner for each of the four specimens, and the average value was taken as the rate of creep change.
- the creep change rate was evaluated in the following three stages. The results are shown in Tables 2-4.
- the urethane resin composition obtained in Examples 3 and 18 to 25 was used in the same manner as in Example 1 or Example 18 except that a 150 ⁇ 125 ⁇ 1 mm molding frame was used as the molding frame.
- a urethane resin molded body was prepared. Then, this molded object was processed into the dimension of length 127mm and width 12.7mm, and it was set as the test body. The test body was marked with markings at 25 mm and 100 mm in the length direction from one end. Five specimens were prepared for each. The test specimen thus prepared was held at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours, and then tested.
- HB horizontal combustion
- the combustion speed during the 75 mm span does not exceed 75 mm / min, or the combustion stops before reaching the 100 mm mark. It is a condition to satisfy.
- the test method was to fix the specimen at the end farthest from the 25 mm mark of the specimen, make the length direction of the specimen horizontal, and incline the width direction by 45 degrees.
- a burner flame was brought into contact with the unfixed end of the test specimen for 30 seconds, and then the burner was removed.
- the burner was immediately moved away from the specimen.
- the time when the burning tip reaches the marked line 25 mm was set to 0 second, and the time was measured in seconds to obtain the burning rate.
- the point where the combustion stopped was measured.
- the results of the flammability test were evaluated in the following three stages.
- the results are shown in Tables 2-4.
- the results shown in Tables 2 to 4 are evaluated as “3” when, for example, all of the five tests satisfy the following “3”, and the following “2” is evaluated even once among the five tests. In the case of the evaluation, “2” was evaluated. In other words, the results shown in Tables 2 to 4 show the lowest evaluation results among the five tests.
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Abstract
Description
このような制振材として、例えば、特許文献1には、アクリルウレタン樹脂を含む材料が記載されている。
また、特許文献2には、振動エネルギーを吸収、低減、抑制することが可能な粒子と、バインダー樹脂とを含有する樹脂組成物が記載され、この粒子として、架橋樹脂からなるシェルを有するコアシェル粒子が記載されている。
また、有機樹脂で形成された外殻を有するマイクロカプセルや有機樹脂で形成された多孔体を配合した制振性樹脂組成物から得られる成形体は、外殻の樹脂が非常に強固な構造であるため、変形しにくく、振動エネルギーを熱エネルギーに変換しにくいという問題点があった。
本発明の構成例は、以下の[1]~[16]である。
[6] 前記相変化物質の融点が-30~200℃である、[1]~[5]のいずれかに記載の制振性ウレタン樹脂組成物。
[9] さらに難燃剤(E)を含有する、[1]~[8]のいずれかに記載の制振性ウレタン樹脂組成物。
[10] さらに添加剤(F)を含有する、[1]~[9]のいずれかに記載の制振性ウレタン樹脂組成物。
(1)80℃、1Hzにおける損失係数(tanδ)が0.4以上
(2)70℃下、4.5MPaの荷重を1週間加えた時のクリープ変化率が25%以下
[14] さらに、下記(3)の要件を満たす、[13]に記載の制振性ウレタン樹脂成形体。
(3)燃焼性がUL94規格のHB基準を満たす
本発明の制振性ウレタン樹脂組成物(以下「本発明の組成物」ともいう。)は、ひまし油系ポリオール(A)、イソシアネート(B)および相変化物質を内包する無機粒子(C)を含有し、必要により、本発明の効果を損なわない範囲で無機顔料(D)、難燃剤(E)および添加剤(F)を含有してもよい。
ひまし油は、トウダイグサ科のトウゴマという植物の種子から得られる淡黄色の粘調な不乾性油である。ひまし油は、脂肪酸中の約90%がリシノール酸であり、一分子中に水酸基、二重結合およびエステル結合を有しているため、他の植物油脂とは異なるユニークな特徴を有する。その特長としては、優れた安定性、可撓性、電気絶縁性、耐水性、耐衝撃性等が挙げられる。本発明の組成物は、このような特徴を有するひまし油を出発原料として用いたひまし油系ポリオールを含有することにより、摩擦や衝撃といった機械的応力への耐性に加え、耐熱性、耐加水分解性、耐酸性に優れる成形体を形成することができる。
また、ひまし油系ポリオール(A)を用いることで、熱変形や硬化収縮が起こりにくい成形体を形成することができる。
これに対し、本発明では、ひまし油系ポリオール(A)を用いることで、前記の効果を奏する成形体を得ることができる。
市販品としては、URIC H-102、URIC H-92、URIC H-81、URIC H-73X、URIC H-62、URIC H-420、URIC H-854、URIC H-870、URIC H-1824、URIC AC-006、URIC Y-406、URIC HF-2009(以上、伊藤製油(株)製)、HS CM-075P、HS PPE-12H、HS 3P-255、HS 3G-500B、HS 2B-5500、HS 2G-120、TLM、HS CM(以上、豊国製油(株)製)などが挙げられる。
水酸基価および官能基数が前記範囲にあるひまし油系ポリオール(A)を用いることで、制振性および耐クリープ性にバランスよく優れる成形体を得ることができ、さらに、架橋密度が大きくなり、高強度、かつ耐熱性に優れたクリープ変化率の小さい成形体を得ることができる。また、水酸基価および官能基数が前記範囲にあるひまし油系ポリオール(A)を用いることで、高温下でも高い損失係数を示す成形体を得ることができる。
なお、前記官能基数とは、ひまし油系ポリオール(A)1分子中の水酸基の数を表す。
前記Mnは、ひまし油系ポリオール(A)の水酸基価を基に計算し求めることができる。
一般的には、ひまし油系ポリオール(A)はMnが大きいほど粘度は高くなる傾向にある。
ひまし油系ポリオール(A)は、1種のみを用いてもよいし、2種以上を用いてもよい。
前記イソシアネート(B)は、前記ひまし油系ポリオール(A)と反応し、硬化可能な化合物であればよい。このようなイソシアネート(B)としては、ジフェニルメタンジイソシアネート(以下「MDI」と略称する。〔例:2,2’-MDI、2,4’-MDI、4,4’-MDI、ポリメリックMDI(クルードMDI)〕)、トリレンジイソシアネート(以下「TDI」と略称する。〔例:2,4-TDI、2,6-TDI〕)、ナフタレンジイソシアネート等の芳香族ポリイソシアネート類のほか、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート等の脂肪族ポリイソシアネート類、前記ポリイソシアネートのカルボジイミド変性体、およびイソシアネート化合物と低分子ポリオールなどとを反応させて得られるポリウレタン系プレポリマーなどが挙げられる。
なお、市販品には、前記イソシアネートを主成分として含み、さらに該イソシアネートの異性体等を含む場合や溶剤を含む場合があり、本発明では、これらの市販品を特に制限なく使用することができるが、機械的強度、耐クリープ性に優れ、熱変形や硬化収縮が起こりにくい成形体を形成できるなどの点で無溶剤型イソシアネートであることが好ましい。
イソシアネート(B)は、1種のみを用いてもよいし、2種以上を用いてもよい。
前記相変化物質を内包する無機粒子(C)としては、無機粒子の内部に相変化物質を内包している粒子であれば特に制限されず、具体的には、相変化物質を内包し、無機物質で形成された外殻を有するマイクロカプセルや無機物質で形成された多孔性粒子の細孔内に相変化物質が充填されている粒子などが挙げられる。つまり、前記無機粒子(C)としては、相変化物質が無機物質の外殻に完全に覆われている場合のみならず、相変化物質が無機物質で形成された多孔性粒子の細孔内に捕捉された状態であり、外部に接しうる状態にあってもよい。
前記無機粒子(C)を用いることで、荷重により変形しやすく、振動エネルギーを熱エネルギーに変換しやすい成形体を得ることができる。このため、該成形体は、制振効果、耐クリープ性および耐熱性などに優れる。
これに対し、本発明では、前記無機粒子(C)を用いることで、前記の効果を奏する成形体を得ることができる。
一方、本発明の組成物では、前記無機粒子(C)を用いることで、ウレタン樹脂組成物中に該粒子(相変化物質)を均一分散させることができ、このために、前記効果を奏すると考えられる。
なお、前記多孔性粒子としては、その表面から内部にかけて貫通する細孔を有する無機物質からなる粒子が挙げられ、その内部に空洞を有する中空粒子であってもよく、空洞を有していない粒子であってもよい。
無機粒子に内包される相変化物質は、1種単独であってもよく、または2種以上でもよい。
無機粒子(C)は、1種のみを用いてもよいし、2種以上を用いてもよい。
本発明の組成物は、クリープ変化に対する耐性を向上させるために、無機顔料(D)を含有してもよい。なお、無機顔料(D)は、無機粒子(C)以外の無機物である。無機顔料(D)は、1種のみを用いてもよいし、2種以上を用いることも可能である。
本発明の組成物は、難燃性を向上させるために、難燃剤(E)を含有してもよい。難燃剤(E)は、1種のみを用いてもよいし、2種以上を用いてもよい。
本発明の組成物は、さらに、前記(A)~(E)以外の添加剤(F)を含んでもよい。該添加剤(F)としては、消泡剤、水分吸着剤、触媒およびその他材料等が挙げられる。
添加剤(F)は、1種のみを用いてもよいし、2種以上を用いてもよい。
耐クリープ性に優れる成形体を得る等の点から、該成形体には、気泡が存在していないことが好ましい。このため、本発明の組成物には、消泡剤を配合することが好ましい。
消泡剤の種類としてはシリコーン系消泡剤、ミネラルオイル系消泡剤などが挙げられ、それぞれ水系、溶剤系、無溶剤系が存在する。本発明では、成形体を形成する際の収縮を抑えるために無溶剤のシリコーン系消泡剤が好ましく、この消泡剤を本発明の組成物全量に対して0~3質量%の範囲で含有することが好ましい。無溶剤のシリコーン系消泡剤の市販品としては、例えば、Dоw Corning Toray SAG-47(東レ・ダウコーニング(株)製)が挙げられる。
消泡剤は、1種のみを用いてもよいし、2種以上を用いてもよい。
大気中や、無機粒子(C)や無機顔料(D)に含まれうる水分を系内に取り込んだ組成物から成形体を形成する場合、硬化剤であるイソシアネートと水分が反応し、発泡する可能性がある。この発泡を抑制するために系内の水分を除去することが好ましく、このため、本発明の組成物には、水分吸着剤を配合することが好ましい。
前記水分吸着剤は、本発明の組成物全量に対して0~10質量%の範囲で配合することが好ましい。
水分吸着剤は、1種のみを用いてもよいし、2種以上を用いてもよい。
本発明の組成物は、ひまし油ポリオール(A)とイソシアネート(B)との反応を促進する触媒を含有してもよい。このような触媒の例としては、スズカルボン酸塩、アミン系触媒、スズ以外の金属カルボン酸塩および1,8-ジアザビシクロ[5,4,0]ウンデセン-7(DBU)塩が挙げられる。スズカルボン酸塩としては、ジブチルスズジラウレート、ジブチルスズジアセテートおよびスズオクチレートなどが挙げられ、アミン系触媒の例としては、トリエチルアミン、トリエチレンジアミンおよびテトラメチルブタンジアミンが挙げられ、スズ以外の金属カルボン酸塩の例としては、オクチル酸コバルト、オクチル酸マンガンおよびオクチル酸亜鉛が挙げられ、DBU塩としては、DBU-ステアリン酸塩、DBU-オレイン酸塩およびDBU-ギ酸塩が挙げられる。
触媒は、1種のみを用いてもよいし、2種以上を用いてもよい。
本発明の組成物は、さらに、必要に応じて、湿潤分散剤、表面調整剤、レオロジーコントロール剤、レベリング剤、可塑剤、溶剤等を本発明の目的を損なわない範囲で含有することができる。
これらのその他材料は、それぞれ1種のみを用いてもよいし、2種以上を用いてもよい。
本発明の組成物は、前記(A)~(C)の成分、さらに必要により(D)~(F)の成分を混合することにより調製することができる。本発明の組成物は、貯蔵安定性などの点から、前記(A)成分を含む主剤と前記(B)成分を含む硬化剤からなる2液型であることが望ましい。この場合、無機粒子(C)は、主剤、硬化剤のどちらに配合してもよいが、主剤に配合することが好ましい。さらに、前記無機顔料(D)、難燃剤(E)および添加剤(F)も、主剤、硬化剤のどちらに配合してもよいが、無機顔料(D)および難燃剤(E)は、主剤に配合することが好ましい。また、添加剤(F)のうち、触媒は主剤に配合することが好ましい。
前記主剤と前記硬化剤とを混合することによって、本発明の組成物を調製することができる。
本発明の制振性ウレタン樹脂成形体(以下「本発明の成形体」ともいう。)は、前記本発明の組成物から形成される。
このため、本発明の成形体は、制振効果が高く、かつ、圧縮荷重に対する耐性や耐衝撃性に優れ、熱による塑性変形が少ない。
(1)80℃、1Hzにおける損失係数(tanδ)が0.4以上
(2)70℃下、4.5MPaの荷重を1週間加えた時のクリープ変化率が25%以下
(3)燃焼性がUL94規格のHB基準を満たす
損失係数は、貯蔵せん断弾性率(G’)と損失せん断弾性率(G’’)との比、G’’/G’であり、tanδで表され、本発明の成形体が変形する際に振動エネルギーをどの程度熱エネルギーに変えるかを示す指標である。tanδの値が大きいほど振動エネルギーを熱エネルギーに変換する、つまり制振効果があることを意味する。制振性に優れる成形体が得られる等の点から、80℃、1Hzにおけるtanδは0.4以上であることが好ましく、0.5以上であることがさらに好ましく、0.6以上であることが特に好ましい。
前記損失係数は、具体的には、下記実施例に記載の方法で測定することができる。
樹脂系の材料は、高温雰囲気下で長期間大きな荷重を加え続けると塑性変形することがあり、これをクリープ変化と呼ぶ。70℃の雰囲気下で、4.5MPaの荷重を1週間加えた時のクリープ変化率は、小さければ小さいほどよく、25%以下であることが好ましく、20%未満であることがさらに好ましい。クリープ変化率が25%を超えると、変形に伴い成形体の破断や、亀裂が生じる場合がある。
前記クリープ変化率は、具体的には、下記実施例に記載の方法で測定することができる。
ウレタン樹脂は一般的に燃焼しやすく、燃焼性樹脂に分類される。また、船舶に用いられる材料は、SOLAS(The International Convention for the Safety of Life at Sea)条約により、火災防止の拡大を防ぐことを目的として難燃性が必要とされる。
前記基材としては、コンクリート、モルタル、スレート板、合板、タイル、金属、ガラス、フィルム、繊維等が挙げられ、これらの基材は表面処理が施されていてもよい。
[実施例1]
ひまし油系ポリオールURIC H-102(伊藤製油(株)製)80.0部およびリケンレヂンLA-15-100(三木理研工業(株)製)20.0部を容器に仕込み、マイクロカプセルの外殻を破壊しないようにハイスピードディスパーを用いて500rpm以下で10分間分散を行った。その後、Dow Corning Toray SAG-47(東レ・ダウコーニング(株)製)0.2部、モレキュラーシーブ4Aパウダー(ユニオン昭和(株)製)3.0部、10%グレックTL(DIC(株)製)0.1部を順次加えて撹拌し、主剤を調製した。そこに、主剤に対してNCO/OH=1.06となるように、硬化剤としてミリオネートMTL(日本ポリウレタン工業(株)製)70.1部を加え、混合後、脱泡してウレタン樹脂組成物を調製した。
原料の種類および使用量を表2または4に示す通りに変更した以外は実施例1と同様にして、ウレタン樹脂組成物を調製し、得られた組成物を用いた以外は実施例1と同様にしてウレタン樹脂成形体を作成した。なお、表2または4の各材料の詳細は、表1に示すとおりである。
ひまし油系ポリオールURIC H-81(伊藤製油(株)製)80.0部およびExolit AP462(CLARIANT製)を15.0部容器に仕込み、ハイスピードディスパーを用いて1000rpmで15分間分散を行った。その後、リケンレヂンLA-15-100(三木理研工業(株)製)20.0部を配合し、マイクロカプセルの外殻を破壊しないようにハイスピードディスパーを用いて500rpm以下で10分間分散を行った。分散工程を終了後、Dow Corning Toray SAG-47(東レ・ダウコーニング(株)製)0.3部、モレキュラーシーブ4Aパウダー(ユニオン昭和(株)製)3.0部、10%グレックTL(DIC(株)製)0.1部を順次加えて撹拌し、主剤を調製した。そこに、主剤に対してNCO/OH=1.06となるように、硬化剤としてミリオネートMTL(日本ポリウレタン工業(株)製)74.5部を加え、混合後、脱泡してウレタン樹脂組成物を調製した。
原料の種類および使用量を表3に示す通りに変更した以外は実施例18と同様にして、ウレタン樹脂組成物を調製し、得られた組成物を用いた以外は実施例18と同様にしてウレタン樹脂成形体を作成した。なお、表3の各材料の詳細は、表1に示すとおりである。
実施例1~25および比較例1~7で作成したウレタン樹脂成形体を用いて、損失係数tanδの測定を行った。損失係数の測定は、装置として、「(株)島津製作所製、島津サーボパルサ EHF-EG10-20L型」、ソフトウェアとして「島津サーボパルサ 4830型制御装置」の疲労・耐久試験モードを用いて実施した。試験温度は80℃とし、1Hzの周波数の振動をウレタン樹脂成形体に加えながら、圧縮方向に5kNの荷重を加え、1kNまで除荷するというサイクルを1サイクルとして、このサイクルを1000サイクル繰り返すことで、損失係数を測定した。損失係数の結果は、以下の4段階で評価した。結果を表2~4に示す。
3:0.5≦tanδ<0.6
2:0.4≦tanδ<0.5
1:tanδ<0.4
評価2~4を合格○とし、評価1を不合格×とした。
成形枠として、100×100×5mmの成形枠を用いた以外は、実施例1または実施例18と同様にして、実施例1~25および比較例1~7で得られたウレタン樹脂組成物を用いて、それぞれウレタン樹脂成形体を作成した。作成したウレタン樹脂成形体をASTM D621に準拠した方法で養生した。養生後、成形体から5×5×5mmの大きさの試験体を4個切り出し、70℃の雰囲気下で、該試験体の厚さ方向に4.5MPaの荷重を1週間加えた。荷重を加える前と、荷重を加えてから1週間後の試験体の厚さを測定し、荷重を加える前後における試験体の厚さ方向の変化率を算出した。4個の試験体それぞれについて同様に変化率を測定し、その平均値をクリープ変化率とした。また、クリープ変化率を以下の3段階で評価した。結果を表2~4に示す。
2:20≦クリープ変化率≦25%
1:試験体が破断、または荷重を加えた直後に変形
評価2および3を合格○とし、評価1を不合格×とした。
成形枠として、150×125×1mmの成形枠を用いた以外は、実施例1または実施例18と同様にして、実施例3および18~25で得られたウレタン樹脂組成物を用いて、それぞれウレタン樹脂成形体を作成した。その後、該成形体を、長さ127mm、幅12.7mmの寸法に加工し、試験体とした。試験体には、片端から長さ方向に25mmおよび100mmのところに標線をつけた。試験体はそれぞれ5個作成した。作成した試験体を温度23℃および50%の相対湿度で、48時間保持後、試験を行った。
HB基準を満たす試験体は、
1.試験体の厚さが3.0mm~13mmの場合、75mmスパン間の燃焼速度が40mm/minを超えないこと、
2.試験体の厚さが3.0mm未満の場合、75mmスパン間の燃焼速度が75mm/minを超えないこと、または、
3.試験体の厚さによらず、100mmの標線に達する前に燃焼が止まること、
が条件となる。
2:燃焼速度≦75mm/min、または、100mmの標線に達する前に燃焼が止まること
1:燃焼速度>75mm/min、且つ、100mmの標線まで燃焼すること
評価2および3を合格○とし、評価1を不合格×とした。
Claims (16)
- ひまし油系ポリオール(A)、イソシアネート(B)および相変化物質を内包する無機粒子(C)を含有する制振性ウレタン樹脂組成物。
- 前記ひまし油系ポリオール(A)の水酸基価が300mgKOH/g以上であり、かつ官能基数が3以上である、請求項1に記載の制振性ウレタン樹脂組成物。
- 前記ひまし油系ポリオール(A)の25℃における粘度が8,000mPa・s以下である、請求項1または2に記載の制振性ウレタン樹脂組成物。
- 前記無機粒子(C)を1~25質量%含有する、請求項1~3のいずれか1項に記載の制振性ウレタン樹脂組成物。
- 前記相変化物質が、パラフィン、ワックス、脂肪酸およびポリアルキレングリコールから選択される少なくとも1種である、請求項1~4のいずれか1項に記載の制振性ウレタン樹脂組成物。
- 前記相変化物質の融点が-30~200℃である、請求項1~5のいずれか1項に記載の制振性ウレタン樹脂組成物。
- 前記イソシアネート(B)が、カルボジイミド変性ジフェニルメタンジイソシアネートおよびトリレンジイソシアネートから選択される少なくとも1種である、請求項1~6のいずれか1項に記載の制振性ウレタン樹脂組成物。
- さらに無機顔料(D)を含有する、請求項1~7のいずれか1項に記載の制振性ウレタン樹脂組成物。
- さらに難燃剤(E)を含有する、請求項1~8のいずれか1項に記載の制振性ウレタン樹脂組成物。
- さらに添加剤(F)を含有する、請求項1~9のいずれか1項に記載の制振性ウレタン樹脂組成物。
- 2液型である、請求項1~10のいずれか1項に記載の制振性ウレタン樹脂組成物。
- 請求項1~11のいずれか1項に記載の制振性ウレタン樹脂組成物から形成された制振性ウレタン樹脂成形体。
- 下記(1)および(2)の要件を満たす制振性ウレタン樹脂成形体。
(1)80℃、1Hzにおける損失係数(tanδ)が0.4以上
(2)70℃下、4.5MPaの荷重を1週間加えた時のクリープ変化率が25%以下 - さらに、下記(3)の要件を満たす、請求項13に記載の制振性ウレタン樹脂成形体。
(3)燃焼性がUL94規格のHB基準を満たす - 船舶のエンジン下部に使用される、請求項12~14のいずれか1項に記載の制振性ウレタン樹脂成形体。
- 請求項1~11のいずれか1項に記載の制振性ウレタン樹脂組成物を施工箇所に流し込んで成形体を形成する工程を含む、制振性ウレタン樹脂成形体の形成方法。
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2015
- 2015-08-25 EP EP15835078.5A patent/EP3187520B1/en active Active
- 2015-08-25 KR KR1020177003888A patent/KR101876155B1/ko active IP Right Grant
- 2015-08-25 WO PCT/JP2015/073889 patent/WO2016031825A1/ja active Application Filing
- 2015-08-25 CN CN201580045743.3A patent/CN106795265B/zh active Active
- 2015-08-25 JP JP2016545551A patent/JP6253790B2/ja active Active
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2017
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JP2001288240A (ja) * | 2000-04-07 | 2001-10-16 | Bridgestone Corp | 蓄熱性軟質低反発性ポリウレタンフォーム及びその製造方法 |
JP2005289043A (ja) * | 2004-03-09 | 2005-10-20 | Sk Kaken Co Ltd | 制振性積層体 |
JP2009286816A (ja) * | 2008-05-27 | 2009-12-10 | Sumika Bayer Urethane Kk | 自動車内装材用定温保持ポリウレタン樹脂成形品の製造法及び成形品 |
Non-Patent Citations (1)
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See also references of EP3187520A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018060266A1 (en) * | 2016-09-30 | 2018-04-05 | Covestro Deutschland Ag | Resin composition for damping materials |
CN109863187A (zh) * | 2016-09-30 | 2019-06-07 | 科思创德国股份有限公司 | 用于阻尼材料的树脂组合物 |
US10954381B2 (en) | 2016-09-30 | 2021-03-23 | Covestro Deutschland Ag | Resin composition for damping materials |
CN109863187B (zh) * | 2016-09-30 | 2021-12-31 | 科思创德国股份有限公司 | 用于阻尼材料的树脂组合物 |
JP2021091848A (ja) * | 2019-12-03 | 2021-06-17 | スターライト工業株式会社 | 無溶剤系制振性塗料、塗装方法及び塗工物 |
Also Published As
Publication number | Publication date |
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KR20170029599A (ko) | 2017-03-15 |
PH12017500377A1 (en) | 2017-07-17 |
CN106795265A (zh) | 2017-05-31 |
EP3187520B1 (en) | 2021-02-24 |
PH12017500377B1 (en) | 2017-07-17 |
KR101876155B1 (ko) | 2018-07-06 |
JPWO2016031825A1 (ja) | 2017-06-15 |
EP3187520A4 (en) | 2018-04-25 |
CN106795265B (zh) | 2019-05-14 |
EP3187520A1 (en) | 2017-07-05 |
JP6253790B2 (ja) | 2017-12-27 |
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