JP4501441B2 - Damping material for soundproofing and soundproofing sheet using the same - Google Patents

Description

  The present invention relates to a vibration damping material for soundproofing and a soundproofing sheet using the same.

  In recent years, comfort in indoor environments and living spaces has been demanded, and noise countermeasures have become a major problem. As one of the issues, there is prevention of unpleasant noise and resonance sound generated from piping such as water supply pipes and drainage pipes, but as a soundproof sheet with these tubular bodies as adherends, not only has a high soundproofing effect, In order to wind around the outer periphery of the tubular body in a good state, winding workability and adhesion that can follow the shape of the adherend are required.

  Conventional soundproof sheets are laminated products of sound-absorbing layers made of foam, vibration-damping layers made of vinyl chloride resin and rubber, sound insulation layers made of vinyl chloride resin and filler, and heat-shrinkable films. (Patent Document 1). However, with such a soundproof sheet, the soundproofing effect is not sufficient, and for the purpose of enhancing the soundproofing effect, if the filler is further added to the vibration damping layer or the filler added to the soundproofing layer is increased, There is a problem that flexibility is lowered and winding workability and adhesion to a tubular adherend are lowered.

  A soundproof sheet made of a laminate of a first foamed layer, a vibration damping layer made of unvulcanized EPDM rubber, a second foamed layer, and a skin layer has been proposed (Patent Document 2). Such a soundproof sheet uses unvulcanized EPDM rubber for the vibration damping layer, thereby improving the flexibility of the vibration damping layer and improving the winding workability around the tubular adherend. It cannot be wound well around the outer periphery of a pipe with a large curvature, and the flexibility cannot be said to be sufficiently improved.

Japanese Patent Laid-Open No. 10-96496 JP 2003-222289 A

  The present invention relates to a soundproof sheet having a high soundproofing effect and excellent in winding workability and adhesion to an adherend, and a soundproofing material having a high vibration damping effect and excellent flexibility suitable for the soundproofing sheet. The main purpose is to provide

  As a result of intensive studies in view of the above circumstances, the present inventors have determined that a specific amount ratio of an aromatic vinyl-isoprene block copolymer having two or more polyaromatic vinyl blocks and a polyisoprene having a specific weight average molecular weight. It was found that the above-mentioned object can be achieved by using the thermoplastic elastomer composition contained in the above as a vibration damping material for soundproofing, and the present invention has been completed based on this finding.

Thus, according to the present invention, the following inventions (1) and (2) are provided.
(1) (a) a polyaromatic vinyl block possess two or more aromatic vinyl-vinyl bond content in the isoprene units is 20 wt% or less - isoprene block copolymer 20 to 85 wt%, (b A thermoplastic elastomer composition containing 5 to 75% by weight of an aromatic vinyl-isoprene diblock copolymer and (c) 2 to 66% by weight of polyisoprene having a weight average molecular weight of 5,000 to 100,000. A damping material for soundproofing. (2) A soundproofing sheet comprising a vibration damping layer made of the soundproofing damping material according to (1) above.

  ADVANTAGE OF THE INVENTION According to the present invention, a soundproof sheet having a high soundproofing effect and excellent in winding workability and adhesion to an adherend, and a soundproofing control suitable for the soundproofing sheet, having a high vibration damping effect and excellent in flexibility. Shaking material is provided.

A. Soundproofing damping material The soundproofing damping material of the present invention comprises (a) 10 to 98% by weight of an aromatic vinyl-isoprene block copolymer having two or more polyaromatic vinyl blocks, and (b) aromatic vinyl. -It comprises a thermoplastic elastomer composition containing 0 to 88% by weight of an isoprene block copolymer, and (c) 2 to 66% by weight of polyisoprene having a weight average molecular weight of 5,000 to 300,000. Yes.

  The sound-damping material of the present invention formed by molding a thermoplastic elastomer composition having such a composition not only has a high effect of attenuating vibration in a sound region that can be audible to humans, such as noise, but is also possible. Since it is excellent in flexibility, a soundproof sheet excellent in winding workability and adhesion to the adherend can be provided.

  The aromatic vinyl-isoprene block copolymer (a) (hereinafter referred to as “component (a)”) used in the present invention has two or more polyaromatic vinyl blocks, and has at least three polymer blocks. It is what you have.

  The polyaromatic vinyl block in the component (a) refers to a part containing an aromatic vinyl monomer unit as a main constituent unit in the polymer chain of the component (a). The polyaromatic vinyl block preferably has an aromatic vinyl monomer unit content of 80% by weight or more, particularly preferably a homopolymerized aromatic vinyl monomer.

  Examples of the aromatic vinyl monomer include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, p-tert-butyl styrene, and the like. It is done. Of these, styrene can be preferably used.

  If the polyaromatic vinyl block in the component (a) is within a range that does not substantially impair the effects of the present invention, an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer May be copolymerized. Examples of monomers copolymerizable with the aromatic vinyl monomer include conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Preferably mentioned.

  The weight average molecular weight of the polyaromatic vinyl block in the component (a) is preferably 8,000 to 100,000, more preferably 12,000 to 70,000, particularly preferably 14,000 to 50,000. . If the weight average molecular weight of the polyaromatic vinyl block is too small, the shape retention as a sound-damping material tends to be lowered. Conversely, if the weight is too large, the fluidity of the thermoplastic elastomer composition is deteriorated and the moldability is deteriorated. Tend to be inferior.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyaromatic vinyl block in the component (a) is preferably 2 or less, and is 1.5 or less. Is more preferable.

  The polyisoprene block in the component (a) refers to a part containing an isoprene unit as a main constituent unit in the polymer chain of the component (a). The polyisoprene block preferably has an isoprene unit content of 80% by weight or more, and is particularly preferably a homopolymerized isoprene.

  The polyisoprene block in component (a) may be a copolymer of isoprene and a monomer copolymerizable with isoprene as long as the effects of the present invention are not substantially inhibited. As the monomer copolymerizable with isoprene, the above aromatic vinyl monomer; conjugates other than isoprene such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. Preferred are diene monomers.

  The aromatic vinyl monomer unit content of the component (a) is usually 5 to 75% by weight, preferably 10 to 50% by weight, and more preferably 13 to 40% by weight.

  The vinyl bond content in the isoprene unit in the component (a) is not particularly limited, and is usually 50% by weight or less, preferably 20% by weight or less, more preferably 5 to 10% by weight.

  The weight average molecular weight of the component (a) is preferably 100,000 to 1,000,000, more preferably 110,000 to 920,000, particularly preferably 120,000 to 880,000.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (a) is preferably 2 or less, and more preferably 1.5 or less.

  The proportion of the component (a) in the thermoplastic elastomer composition is 10 to 98% by weight, preferably 20 to 94% by weight, more preferably 35 to 85% by weight. If this ratio is too small, the shape retention as a sound damping material for soundproofing is deteriorated and is not suitable for use. On the other hand, if it is too large, not only the soundproofing effect is inferior, but also the workability and adhesion to the adherend are wound. The soundproof sheet is inferior to that.

  The aromatic vinyl-isoprene diblock copolymer (b) (hereinafter also referred to as “component (b)”), which is optionally contained in the thermoplastic elastomer composition, comprises only one polyaromatic vinyl block. It is a block copolymer consisting of two polyisoprene blocks.

  The polyaromatic vinyl block in the component (b) refers to a part containing an aromatic vinyl monomer unit as a main constituent unit in the polymer chain of the component (b). The polyaromatic vinyl block preferably has an aromatic vinyl monomer unit content of 80% by weight or more, and more preferably comprises only an aromatic vinyl monomer unit.

  Examples of the aromatic vinyl monomer include the same ones as described above. Of these, styrene can be preferably used.

  The polyaromatic vinyl block in the component (b) is within a range that does not substantially impair the effects of the present invention, and an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer May be copolymerized. As the monomer copolymerizable with the aromatic vinyl monomer, the same monomers as described above can be preferably exemplified.

  The weight average molecular weight of the polyaromatic vinyl block in the component (b) is preferably 8,000 to 100,000, more preferably 12,000 to 70,000, particularly preferably 14,000 to 50,000. .

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyaromatic vinyl block in the component (b) is preferably 2 or less, and is 1.5 or less. Is more preferable.

  The polyisoprene block in the component (b) refers to a part containing an isoprene unit as a main constituent unit in the polymer chain of the component (b). The polyisoprene block preferably has an isoprene unit content of 80% by weight or more, and more preferably comprises only an isoprene unit. If the isoprene unit content is too small, the soundproofing effect of the soundproofing sheet obtained tends to be inferior.

  The polyisoprene block in component (b) may be a copolymer of isoprene and a monomer copolymerizable with isoprene, as long as the effects of the present invention are not substantially inhibited. Monomers copolymerizable with isoprene include the above aromatic vinyl monomers; conjugates other than isoprene, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Preferred are diene monomers.

  The aromatic vinyl monomer unit content of the component (b) is usually 5 to 75% by weight, preferably 10 to 50% by weight, and more preferably 13 to 40% by weight.

  The vinyl bond content in the isoprene unit in the component (b) is not particularly limited, and is usually 50% by weight or less, preferably 20% by weight or less, more preferably 5 to 10% by weight.

  The weight average molecular weight of (b) component becomes like this. Preferably it is 50,000-250,000, More preferably, it is 55,000-230,000, Most preferably, it is 60,000-220,000.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (b) is preferably 2 or less, and more preferably 1.5 or less.

  The proportion of the component (b) in the thermoplastic elastomer composition is 0 to 88% by weight, preferably 1 to 75% by weight, more preferably 5 to 55% by weight. If the component (b) is too much, shape retention as a soundproofing damping material tends to decrease. By incorporating the component (b) in the thermoplastic elastomer composition in a proportion within the above range, a soundproof sheet having a better balance between the soundproofing effect and the winding workability and adhesion to the adherend can be obtained.

  (A) The manufacturing method of a component is not specifically limited, Generally a well-known manufacturing method can be employ | adopted, for example, the method of polymerizing a polyaromatic vinyl block and a polyisoprene block sequentially, respectively, by anion living polymerization method, A method can be employed in which a block copolymer having a living active terminal is produced, and then a block copolymer is produced by reacting it with a coupling agent.

  The production method of the component (b) is not particularly limited, and generally known production methods can be employed. For example, a method of sequentially polymerizing a polyaromatic vinyl block and a polyisoprene block by an anion living polymerization method can be employed. .

  In addition, although (a) component and (b) component may each be manufactured separately as mentioned above, each polymerization process is put together into one and is made into a mixture of (a) component and (b) component. It can also be manufactured.

  The polyisoprene (c) (hereinafter also referred to as “component (c)”) used in the present invention has a weight average molecular weight of 5,000 to 300,000, preferably 10,000 to 200,000, more preferably 30,000. 000-100,000. If the weight average molecular weight is too small, the soundproofing effect of the obtained soundproofing sheet is lowered. Conversely, if the weight average molecular weight is too large, the soundproofing sheet is inferior in winding workability and adhesion to the adherend.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (c) is preferably 2 or less, and more preferably 1.5 or less.

  The component (c) contains an isoprene unit as a main constituent unit in the polymer chain. Component (c) preferably has an isoprene unit content of 80% by weight or more, and more preferably comprises only isoprene units.

  Component (c) is preferably a homopolymer of isoprene, but may be a copolymer of isoprene and a monomer copolymerizable with isoprene within a range that does not substantially impair the effects of the present invention. Good. Preferred examples of the monomer copolymerizable with isoprene include the above aromatic vinyl monomers and conjugated diene monomers other than isoprene such as butadiene and 1,3-pentadiene.

  The vinyl bond content in the isoprene unit in the component (c) is not particularly limited, and is usually 50% by weight or less, preferably 20% by weight or less, more preferably 5 to 10% by weight.

  (C) The manufacturing method of a component is not specifically limited, Generally a well-known manufacturing method can be employ | adopted, for example, the method of superposing | polymerizing isoprene using an anionic polymerization initiator in a polymerization solvent is employable.

  The proportion of the component (c) in the thermoplastic elastomer composition needs to be 2 to 66% by weight, preferably 5 to 55% by weight, and more preferably 10 to 35% by weight. When the amount of the component (c) is too small, not only is the soundproofing effect inferior, but also the soundproofing sheet is inferior in winding workability and adhesion to the adherend. It will be unsuitable for use.

  In the thermoplastic elastomer composition used in the present invention, the aromatic vinyl monomer unit content in the total amount of the component (a), the component (b) and the component (c) is in the range of 5 to 40% by weight. Is preferable, and it is more preferable that it is in the range of 10 to 30% by weight. If this content is too small, the shape retention as a soundproofing damping material tends to be lowered, and it tends to be difficult to use. Conversely, if it is too large, the workability of winding the obtained soundproof sheet around the adherend and There is a tendency for adhesion to be inferior.

The method for producing the thermoplastic elastomer composition used in the present invention is not particularly limited. The component (a), the component (b) and the component (c), which are separately manufactured, may be kneaded or manufactured by mixing them in a solution, separating the polymer and drying. May be.
You may mix and manufacture the (c) component manufactured separately with what was manufactured as a mixture of (a) component and (b) component.

  The thermoplastic elastomer composition used in the present invention, if necessary, in addition to elastomers other than (a) component, (b) component and (c) component, generally known thermoplastic resins, tackifying resins, Filler, reinforcing fiber, softener, foaming agent, foaming aid, antioxidant, flame retardant, antibacterial agent, light stabilizer, ultraviolet absorber, dye, pigment, lubricant, antiblocking agent, slip agent, antistatic agent Etc. can be blended in a desired amount.

  Examples of the elastomer other than the component (a), the component (b), and the component (c) include, for example, a styrene-butadiene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, and a styrene-ethylene-propylene- Styrene block copolymer, styrene-butadiene random copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene copolymer, ethylene-octene copolymer Polymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, chlorinated polyethylene, polybutadiene rubber, polyisobutylene rubber, polyisoprene rubber, natural rubber, acrylic rubber, chloroprene rubber, silicone rubber, fluororubber, Ureta Rubber, polyurethane-based thermoplastic elastomers, polyamide thermoplastic elastomers, and polyester-based thermoplastic elastomer.

  Examples of the thermoplastic resin include polyethylene and modified products thereof, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyphenylene ether, and the like.

  Tackifying resins are roughly classified into natural resin-based tackifying resins and synthetic resin-based tackifying resins. Examples of natural resin-based tackifier resins include rosin resins and terpene resins. Examples of rosin resins include rosins such as gum rosin, tall rosin and wood rosin; modified rosins such as hydrogenated rosin, disproportionated rosin and polymerized rosin; rosin esters such as glycerin ester and pentaerythritol ester of modified rosin Is done. Examples of terpene resins include terpene resins such as α-pinene, β-pinene, and dipentene (limonene), as well as aromatic modified terpene resins, hydrogenated terpene resins, terpene phenol resins, and the like.

  Synthetic resin tackifying resins are broadly classified into addition polymerization tackifying resins and polycondensation tackifying resins. As addition polymerization type tackifying resin, aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, copolymer (C5-C9) petroleum resin, hydrogenated petroleum resin, alicyclic Petroleum resins such as petroleum resins; coumarone-indene resins; pure monomer-based petroleum resins such as styrene and substituted styrene. Examples of the polycondensation-based tackifying resin include phenolic resins such as alkylphenol resins and rosin-modified phenolic resins, and xylene resins. These tackifier resins may be used alone or in combination of two or more.

  Examples of the filler include clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide, mica, graphite, aluminum hydroxide, various metal powders, wood powder, glass powder, and ceramic powder. In addition, inorganic hollow fillers such as glass balloons and silica balloons; organic hollow fillers made of polystyrene, polyvinylidene fluoride, polyvinylidene fluoride copolymers, and the like.

  Examples of the reinforcing fiber include short fibers and long fibers such as straw, hair, glass fiber, metal fiber, and various other polymer fibers.

  Examples of the softening agent include extension oils such as aromatic process oils, paraffinic process oils, and naphthenic process oils; liquid polymers such as polybutenes and polyisobutylenes.

  Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol and pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. Hindered phenol compounds; thiodicarboxylate esters such as dilauryl thiodipropionate and distearyl thiodipropionate; tris (nonylphenyl) phosphite, 4,4′-butylidene-bis (3-methyl-6) Phosphites such as -tert-butylphenyl) ditridecyl phosphite.

  Examples of the lubricant include hydrocarbon lubricants such as paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, and montan wax; stearic acid, hydroxystearic acid, complex stearic acid, fatty acid lubricant such as hardened oil; Stearamide, oxystearamide, oleylamide, erucylamide, laurylamide, palmitylamide, behenamide, methylolamide, monoamide of higher fatty acids, methylene bissteramide, ethylene bissteramide, ethylene bisoleylamide, ethylene bislaurylamide, higher Fatty acids such as fatty acid bisamide, N-stearyl oleylamide, N-stearyl erucylamide, N-stearyl palmitoamide, complex amide, special fatty acid amide Bromide-based slip material;

  Fatty acid ester-based lubricants such as n-butyl stearate, polyhydric alcohol fatty acid ester, saturated fatty acid ester, ester wax, special fatty acid ester, aromatic fatty acid ester, complex ester system; higher alcohol, higher alcohol complex type, Fatty alcohol-based lubricants such as higher alcohol esters, polyhydric alcohols, polyglycols, polyglycerols; partial ester-based lubricants of fatty acids and polyhydric alcohols such as glycerin fatty acid esters, hydroxystearic acid triglycerides, fatty acid partial esters; Silicone oil, polyorganosiloxane, distearyl epoxy hexohydroxyphthalate, sodium alkyl sulfate, long chain aliphatic compound, nonionic ester activator, ethylene oxide and propylene oxide Block copolymers, and the like tetrafluoroethylene resin powder. These lubricants can be used alone or in combination of two or more.

  The vibration damping material for soundproofing of the present invention is produced by molding the above-described thermoplastic elastomer composition. Examples of the molding method include an injection molding method (insert molding method, two-color molding method, sandwich molding method, gas ink injection molding method, etc.), extrusion molding method, inflation molding method, T-die film molding method, laminate molding method, Examples thereof include blow molding, hollow molding, compression molding, calendar molding, rotational molding, transfer molding, vacuum molding, powder slush molding, and cast molding.

  The shape of the damping material for soundproofing is not particularly limited, and examples thereof include a sheet shape and a packing shape. For example, when used for a soundproofing sheet, the shape following property to the adherend is high. It is preferable that In this case, the thickness of the sheet is preferably 20 μm to 10 cm, more preferably 50 μm to 5 cm. If the thickness is too large, the shape followability to the adherend may be deteriorated. On the other hand, if the thickness is too small, a sufficient vibration damping effect may not be obtained depending on the sound.

  Such a soundproofing damping material of the present invention has a high effect of attenuating the vibration in the sound region and is excellent in the soundproofing effect. In addition, as shown in the embodiment, the soundproofing effect is measured by measuring how much noise is attenuated with the soundproof sheet provided, and the attenuation value (Δdb) is compared with the state without the soundproof sheet provided. It can be evaluated by seeking.

  Further, since the sound damping material for soundproofing of the present invention is extremely excellent in flexibility, for example, the winding workability is good even on an adherend having a large curvature such as a pipe, and the adhesiveness is excellent. A soundproof sheet is obtained.

  Furthermore, since the sound-damping material of the present invention itself has adhesiveness, for example, a sound-proof sheet using the sound-damping material is provided on the bonding surface with the adherend and other functional layers. There is no need to provide an adhesive layer, and the mounting workability is excellent. Moreover, adhesiveness can also be improved by mix | blending the tackifying resin mentioned above in a thermoplastic elastomer composition.

B. Soundproofing sheet The soundproofing sheet of the present invention is characterized by having a vibration damping layer made of the above-mentioned sound damping material for soundproofing. The soundproof sheet of the present invention exhibits a high soundproofing effect by effectively absorbing and attenuating vibrations in a sound region such as noise by the vibration damping layer made of the soundproofing damping material.

  FIG. 1 is a schematic cross-sectional view showing a state in which an example of a soundproof sheet of the present invention is attached to an adherend 20 that is a source of sound 10. For example, as shown to Fig.1 (a), the sound-insulation sheet | seat of this invention may be comprised only from the damping layer 1. FIG.

  Moreover, as shown in FIG.1 (b), the sound-insulation sheet | seat of this invention may consist of the damping layer 1 and the sound absorption layer 2, and as shown in FIG.1 (c), the damping layer 1 is shown. And the sound insulation layer 3 may be used.

  Furthermore, as shown in FIG. 1 (d), the soundproofing sheet of the present invention includes a vibration damping layer 1, a sound absorbing layer 2 formed on the vibration damping layer 1, and a sound insulating layer formed on the sound absorbing layer 2. As shown in FIG. 1 (e), the vibration damping layer 1, the sound insulation layer 3 formed on the vibration suppression layer 1, and the sound insulation layer 3 are formed. The sound absorbing layer 2 may be formed.

  By combining the damping layer 1, the sound absorbing layer 2, and the sound insulating layer 3 in this manner, first, the vibration in the region of the sound 10 generated from the adherend 20 is absorbed in the damping layer 1, and the damping layer 2 The soundproofing effect can be further enhanced by absorbing the sound transmitted through 1 and further blocking the sound transmitted through the sound absorbing layer 2 in the sound insulating layer 3.

  Although FIG. 1 shows an example in which the damping layer 1 is joined to the adherend 20, the soundproof sheet of the present invention is not limited to such a configuration, and the sound absorbing layer 2 and the sound insulating layer 3. May be bonded to the adherend 20, and the damping layer 1 may be formed between the sound absorbing layer 2 and the sound insulating layer 3.

  Although not shown, the soundproof sheet of the present invention may have other functional layers in addition to the sound absorbing layer 2 and the sound insulating layer 3. Further, an adhesive layer may be provided on the joint surface with the adherend 20, and a skin layer may be provided as the outermost layer. Further, intermediate layers such as an adhesive layer and an undercoat layer may be provided between the respective layers, for example, for the purpose of improving adhesiveness.

  Hereinafter, the vibration damping layer, the sound absorbing layer, and the sound insulating layer constituting the soundproof sheet of the present invention will be described.

  The vibration damping layer used in the soundproof sheet of the present invention is made of the above soundproofing vibration damping material. Therefore, the vibration damping layer is excellent in flexibility, and can be easily deformed to follow the shape when bonded to the adherend.

  The shape of the damping layer is not particularly limited as long as it does not impair the damping effect. However, the shape of the damping layer is preferably a sheet because of its high shape followability to the adherend.

  The sound absorbing layer that can be used in the present invention exhibits a soundproofing effect by utilizing the fact that sound energy vibrates air inside the porous material and heat is lost due to friction with the inner wall surface of the pore. Yes, the soundproofing effect of the soundproofing sheet of the present invention can be enhanced by laminating this sound absorbing layer.

  As the sound absorbing layer, commonly known materials can be used as the sound absorbing layer of the soundproof sheet, but it is preferable to use a polymer foam because of its high sound absorbing effect.

  Examples of the polymer foam include polyolefin resin foams such as polyethylene resin foam and polypropylene resin foam, synthetic resin foams such as polystyrene resin foam and soft vinyl chloride resin foam, and styrene-butadiene copolymer. Examples thereof include synthetic rubber foams such as polymer rubber foam and chloroprene rubber foam, and rubber foams such as natural rubber foam. Among them, polyethylene resin foam and polystyrene resin foam are preferably used. These polymer foams may be used individually by 1 type, and may use 2 or more types together.

  The expansion ratio of the polymer foam is preferably 10 to 250 times, more preferably 20 to 200 times. If the expansion ratio is too small, it may be difficult to obtain a sufficient sound absorbing effect. Conversely, if the expansion ratio is too large, the foam tends to be deformed or broken. The shape of the bubbles in the polymer foam may be a closed-cell shape or an open-cell shape, but the latter is preferred in terms of a high sound absorption effect.

  As the sound absorbing layer, for example, natural fibers such as cellulose fibers and cotton; synthetic polymer fibers such as polyamide fibers and polyester fibers; inorganic fibers such as glass fibers and metal fibers; A quality material can also be used.

  Although the thickness of a sound absorption layer is suitably determined according to a use, Preferably it is 100 micrometers-200 mm, More preferably, it is 1 mm-100 mm. If the thickness is too large, the winding workability on the adherend having a large curvature may be deteriorated. Conversely, if the thickness is too small, the sound absorbing effect may not be sufficiently obtained depending on the sound.

  The sound insulation layer that can be used in the present invention has a soundproofing effect by blocking sound transmitted by air vibration, and the soundproofing effect of the soundproofing sheet of the present invention can be improved by providing this sound insulation layer. .

  As the sound insulation layer, a generally known material can be used as the sound insulation layer of the sound insulation sheet. Specifically, polyolefin resin sheet foams such as polyethylene resin sheets and polypropylene resin sheets, synthetic resin sheets such as soft vinyl chloride resin sheets; EPT rubber sheets, EPDM rubber sheets, styrene-butadiene copolymer rubber sheets, chloroprene Examples thereof include rubber sheets such as rubber sheets and butyl rubber sheets, and rubber sheets such as natural rubber sheets; metal foil such as aluminum, paper, and cloth.

  Moreover, compounding agents, such as a filler, a reinforcing fiber, and a softening agent, can also be mix | blended with a resin sheet or a rubber sheet. As a compounding agent, the same thing as what was illustrated in the column of the said "A. damping material for soundproofing" can be used.

  The thickness of the sound insulation layer is appropriately determined according to the application, but is preferably 20 μm to 100 mm, more preferably 100 μm to 30 mm. If the thickness is too large, the winding workability on the adherend having a large curvature may be deteriorated. Conversely, if the thickness is too small, the soundproofing effect may not be sufficiently obtained depending on the sound.

  The other functional layer that can be used for the soundproofing sheet of the present invention is not particularly limited as long as the soundproofing effect of the soundproofing sheet of the present invention can be enhanced by being laminated with the vibration damping layer.

  Further, the adhesive layer optionally provided in the soundproof sheet of the present invention is appropriately determined according to the use, and is not particularly limited. For example, the thermosetting resin, the thermoplastic resin, the synthetic adhesive, Generally known materials such as natural adhesives can be used. The form may be liquid or solid, and may be either an organic solvent system or an emulsion system.

  Furthermore, the materials of the skin layer and the undercoat layer that can be used in the present invention are not particularly limited, and known materials that are usually used for soundproof sheets can be used.

  The method for producing the soundproof sheet of the present invention is not particularly limited. For example, at least one of the functional layers such as the sound absorbing layer and the sound insulating layer to be laminated has adhesiveness or heat fusion property. If it is, it can be produced by laminating as it is or by heat-sealing.

  On the other hand, when the functional layer itself does not have adhesiveness or heat-fusibility, or when the performance is insufficient, an adhesive layer is formed at the interface and heated as necessary. Thus, the soundproof sheet of the present invention can be manufactured.

  Since the soundproof sheet of the present invention has a vibration damping layer made of the above-mentioned soundproofing vibration damping material, the soundproofing effect is excellent by effectively absorbing the vibration in the sound region. In addition, the soundproof sheet of the present invention is excellent in flexibility, for example, has good winding workability even on an adherend having a large curvature, and has excellent adhesion.

  Such soundproofing damping materials and soundproofing sheets of the present invention are, for example, flooring materials such as apartments, wall materials, ceilings, window frames, shutters, doors, soundproof walls, roofing materials, piping for water supply pipes and drainage pipes, etc. Building materials such as: Record support turntables, audio equipment such as CD players, OA equipment such as copiers, fax machines, printers, etc .; reduce unpleasant noise and resonance noise, air conditioner outdoor units, sound in ducts, etc. It can be used for the purpose of reducing unpleasant noise and resonance noise generated by the motor drive of home appliances; noise in the car engine room and in the car. Especially, since the adhesiveness with respect to a to-be-adhered body with large curvatures, such as a water supply pipe and a drain pipe, is high, it is especially suitable as soundproof sheets, such as these piping.

  The present invention is not limited to the above-described embodiment. The above-described embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the claims of the present invention. Anything that exhibits the same effect is included in the technical scope of the present invention.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, comparative examples and reference examples, parts and% are based on weight unless otherwise specified.

(1) Hardness The hardness of the obtained vibration-damping material sheet for soundproofing was measured with a JIS A type hardness meter according to JIS K6301.

(2) Soundproofing effect The obtained soundproofing sheet was wrapped around and bonded to the outer periphery of the drainage pipe so that the vibration damping layer and the outer peripheral surface of the domestic wastewater pipe having a nominal diameter of 75 mm were in contact with each other, thereby producing an evaluation pipe. The noise level (db ₁ : decibel) was measured with a noise meter (LA-210, manufactured by Ono Sokki Co., Ltd.) disposed at a position 1 m away from the tube by flowing water through the evaluation tube.
Evaluation was performed by calculating a difference (Δdb = db ₀ −db ₁ ) from the noise level (db ₀ ) when water was passed in a state where no soundproof sheet was applied. The larger this value (Δdb), the higher the soundproofing effect.

(3) Winding workability Winding workability is visually observed when the soundproof sheet is wound around the outer periphery of the drainage pipe so that the vibration damping layer and the outer peripheral surface of the domestic wastewater pipe with a nominal diameter of 75 mm are in contact with each other. Confirmed with. The evaluation criteria were as follows.
○: Wound in good condition △: Hard to wind ×: Not wound

(4) Adhesiveness One minute after applying the adhesion when the soundproof sheet is wound around the outer periphery of the drainage pipe so that the vibration control layer and the outer peripheral surface of the domestic wastewater pipe having a nominal diameter of 75 mm are in contact with each other. Confirmed with. The evaluation criteria were as follows.
○: Wound in good condition △: The edge of the soundproof sheet was peeled off ×: The whole soundproof sheet was peeled off

(Reference Example 1)
Using a pressure-resistant reactor, 112 parts of cyclohexane, 0.000728 parts of N, N, N ′, N′-tetramethylethylenediamine (abbreviated as “TMEDA”) and 11.7 parts of styrene were stirred at 40 ° C. Then, 0.0267 parts of a polymerization initiator n-butyllithium was added, and polymerization was performed for 1 hour while raising the polymerization temperature to 50 ° C. At this time, the polymerization conversion of styrene was 100%. A part of the reaction solution was collected, and the weight average molecular weight of the polystyrene block was measured by gel permeation chromatography.

  Subsequently, 36.3 parts of isoprene was added over 1 hour while controlling the temperature so that the reaction temperature was between 50 ° C. and 60 ° C., and polymerization was further carried out for 1 hour after completion of the addition. The polymerization conversion rate at this point was 100%. A part of the reaction solution was collected, and the weight average molecular weight of the styrene-isoprene diblock copolymer (corresponding to the component (b)) was measured by gel permeation chromatography. .

Next, 0.0242 parts of dimethyldichlorosilane was added as a coupling agent and a coupling reaction was carried out for 2 hours to form a styrene-isoprene-styrene triblock copolymer (corresponding to the component (a)). Thereafter, 0.04 part of methanol was added to the reactor as a polymerization terminator and mixed well, and an aromatic vinyl-isoprene block copolymer composition comprising the above components (a) and (b) (in the table) Then, “(a) + (b) component” is written.) I was obtained. A part of the reaction solution is sampled, and the styrene unit content in the composition I is measured. By gel permeation chromatography, the weight average molecular weight of the entire composition, and the components (a) and (b) The weight ratios of the components were measured and are shown in Table 1. The styrene unit content was determined by ¹ H-NMR measurement.

(Reference Example 2)
TMEDA, n-butyllithium, styrene, isoprene, dimethyldichlorosilane and methanol are changed in the same manner as in Reference Example 1 except that the amounts are changed as shown in Table 1, and consist of component (a) and component (b). Aromatic vinyl-isoprene block copolymer composition II was obtained. The results are shown in Table 1.

(Reference Example 3)
Using a pressure-resistant reactor, 112 parts of cyclohexane, 0.00364 part of TMEDA and 0.134 part of n-butyllithium are stirred at 40 ° C., and 48 parts of isoprene are added over 1 hour while raising the polymerization temperature to 60 ° C. Then, after completion of the addition of isoprene, polymerization was further carried out at 60 ° C. for 1 hour. The polymerization conversion rate of isoprene was 100%. Thereafter, 0.2 parts of methanol as a polymerization terminator was added to the reactor and mixed well to obtain polyisoprene (i). The weight average molecular weight of polyisoprene (i) was 40,000.

Example 1
40 parts of a 30% cyclohexane solution of polyisoprene (i) is added to 100 parts of a 30% cyclohexane solution of the aromatic vinyl-isoprene block copolymer composition I, and the antioxidant 2,6-di-tert-butyl- 0.3 parts of p-cresol was added and mixed, and the mixed solution was added dropwise to warm water heated to 85 to 95 ° C. to volatilize the solvent. The obtained precipitate was pulverized and dried with hot air at 85 ° C. to obtain a thermoplastic elastomer composition (I) containing the component (a), the component (b) and the polyisoprene (i).

  The thermoplastic elastomer composition (I) was kneaded with two rolls heated to 120 ° C. to form a sheet. This sheet-like material was put into a mold, press-molded at 130 ° C. for 10 minutes, cooled and taken out to obtain a 1 mm-thick soundproofing vibration damping sheet.

  A layer of open-cell polyethylene foam sheet (foaming ratio: 100 times) having a thickness of 2 mm is laminated on the vibration-damping material sheet for soundproofing, and a thickness of 0. 0 is formed on the foamed sheet using a chloroprene rubber adhesive. A soundproof sheet was obtained by laminating 5 mm soft vinyl chloride resin sheets. The soundproofing effect, winding workability and adhesion of this soundproofing sheet were measured, and the results are shown in Table 2.

(Example 2)
A thermoplastic elastomer composition as in Example 1 except that 25 parts of a 30% cyclohexane solution of polyisoprene (i) was added to 100 parts of a 30% cyclohexane solution of the aromatic vinyl-isoprene block copolymer composition II. (II) was obtained.
The thermoplastic elastomer composition (II) was kneaded with two rolls heated to 120 ° C. to form a sheet. This sheet-like material was put into a mold, press-molded at 130 ° C. for 10 minutes, cooled and taken out to obtain a 1 mm-thick soundproofing vibration damping sheet. The hardness of the sheet was measured and shown in Table 2.
A soundproof sheet was produced in the same manner as in Example 1 using the above soundproofing vibration damping sheet. The soundproofing effect, winding workability and adhesion of this soundproofing sheet were measured, and the results are shown in Table 2.

(Comparative Example 1)
Add 100 parts of 30% cyclohexane solution of aromatic vinyl-isoprene block copolymer composition I to 0.3 parts of antioxidant 2,6-di-tert-butyl-p-cresol and mix. The solvent was volatilized by adding dropwise to warm water heated to 85-95 ° C. The obtained precipitate was pulverized and dried with hot air at 85 ° C. to obtain a thermoplastic elastomer composition (III) containing no polyisoprene (i).
The thermoplastic elastomer composition (III) was kneaded with two rolls heated to 120 ° C. to form a sheet. This sheet-like material was put into a mold, press-molded at 130 ° C. for 10 minutes, cooled and taken out to obtain a 1 mm-thick soundproofing vibration damping sheet. The hardness of the sheet was measured and shown in Table 2.

  Using a chloroprene rubber adhesive, a 2 mm thick open-celled polyethylene foam sheet (expanding ratio of 100 times) is laminated on the soundproofing vibration damping sheet, and further using a chloroprene rubber adhesive. A soundproof sheet was obtained by laminating a soft vinyl chloride resin sheet having a thickness of 0.5 mm on the foamed sheet. The soundproofing effect, winding workability and adhesion of this soundproofing sheet were measured, and the results are shown in Table 2. In the measurement, a soundproof sheet was adhered to the outer periphery of the domestic wastewater pipe using a chloroprene rubber adhesive.

(Comparative Example 2)
100 parts of EPDM (trade name: EPT3045, manufactured by Mitsui Petrochemical Co., Ltd.) and 400 parts of zinc oxide and 100 parts of talc (trade name: TC talc, manufactured by Tsuchiya Kaolin Industry Co., Ltd.) are mixed and kneaded. And made a sheet. This sheet-like material was put into a mold, press-molded at 120 ° C. for 10 minutes, then cooled and taken out to obtain a 1 mm-thick soundproofing vibration damping sheet. The hardness of the sheet was measured and shown in Table 2.

  A soundproof sheet was produced in the same manner as Comparative Example 1 using the above soundproofing damping material sheet. The soundproofing effect, winding workability and adhesion of this soundproofing sheet were measured, and the results are shown in Table 2. In the measurement, a soundproof sheet was adhered to the outer periphery of the domestic wastewater pipe using a chloroprene rubber adhesive.

It is a schematic sectional drawing which shows the state which affixed on the to-be-adhered body an example of the soundproof sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Damping layer 2 ... Sound absorption layer 3 ... Sound insulation layer 10 ... Sound 20 ... Adhering body

Claims (2)

(A) a polyaromatic vinyl block possess two or more aromatic vinyl-vinyl bond content in the isoprene units is 20 wt% or less - isoprene block copolymer 20 to 85 wt%, (b) aromatic A thermoplastic elastomer composition comprising 5 to 75% by weight of a vinyl-isoprene diblock copolymer and (c) 2 to 66% by weight of polyisoprene having a weight average molecular weight of 5,000 to 100,000. Damping material for soundproofing. A soundproofing sheet comprising a vibration damping layer made of the soundproofing vibration damping material according to claim 1.

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