JP2004162061A - Vibration-damping material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic polymer-based vibration-damping material composition which exhibits large loss modulus (E") and dissipation factor (η) at high temperatures and can be used in a wide range of high temperature. <P>SOLUTION: The vibration-damping material composition comprises (1) an organic polymer matrix material containing a vibration-damping imparting agent or (2) the matrix containing the agent and an inorganic filler and/or an organic filler, the agent being a polyvinyl phenolic resin having repeating units represented by formula [1]. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a vibration-damping material composition, and more specifically, as a material for automobiles, buildings, various industrial machinery, home appliances, medical devices, and the like, or a coating material and other laminated materials, The present invention relates to a vibration damping material composition capable of damping vibration and sound used as a sheet-shaped molded body.

  In the industrialized society in recent years, as the needs for energy saving and low environmental load increase from the viewpoint of global environmental protection, weight reduction of vibration damping materials and sound insulation materials has been strongly demanded.

  However, conventional polymer damping materials having a vibration damping function and a sound insulating function are based on the viscous effect of a viscoelastic material and the friction effect with an inorganic filler, and convert external vibration energy into heat energy. Since vibration absorption is achieved by radiating vibration energy to the outside and losing vibration energy, the vibration damping effect of such a vibration damping material is within a temperature range based on the glass transition point of the polymer compound as a constituent. And it is difficult to arbitrarily control the decay time, and there is a limit in reducing the weight of the material.

  Therefore, as materials capable of solving such difficulties, vibration damping materials in which various organic additives are blended with a polymer material have been proposed. For example, vibration damping materials in which a triazole-based compound or a hindered phenol-based compound or the like is compounded with a polymer as a low molecular compound have been proposed. Among such proposals, according to Patent Document 1 (Japanese Patent Application Laid-Open No. 11-68190), a vibration damping material obtained by blending a benzothiazole compound with chlorinated polyethylene is disclosed in Patent Document 2 (Japanese Patent Application Laid-Open No. 2000-44818). Discloses an attenuation material in which a basic polymer having a basic polar side chain contains a hindered phenol compound or the like.

However, hindered phenol compounds proposed as vibration damping agents have an alkyl group having a large number of carbon atoms such as a butyl group or more, so that interaction with a polymer or an inorganic filler as a matrix material is not strong. Not only does the number of interactions between the damping agent and the polymer decrease, but at high temperatures, the dissociation of the interactions easily occurs, resulting in high loss modulus (E ″) and loss coefficient (E) at high temperatures. η) was not exhibited, and the usable temperature range was narrow. Further, there are still many points to be solved regarding durability for exerting a vibration damping function over a long period of time.
JP-A-11-68190 JP 2000-44818 A

  Accordingly, an object of the present invention is to provide a vibration damping material having a more excellent vibration damping function, that is, a maximum loss elasticity at a high temperature, as compared with a vibration damping material in which a conventionally proposed low molecular compound is blended as a vibration damping agent. Damping material composition having high ratio (E '') and loss coefficient (η), and having a wide range of usable temperature ranges for each of them, and having a durability capable of maintaining the damping function at a high level for a long period of time. To provide things.

  Therefore, the present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, compared with a conventional vibration damping material using a phenolic compound or other low molecular compounds, a matrix material made of an organic polymer has a higher A vibration damping material composition obtained by containing a specific phenolic polymer having a strong interaction exhibits a high loss modulus (E '') and a loss coefficient (η) at high temperatures, and is usable in a temperature range. The present inventors have found that a vibration damping material composition having a wide width can be provided, and have arrived at the present invention based on these findings.

Thus, according to the present invention,
An organic polymer matrix material is a vibration damping material composition containing a vibration damping agent,
The vibration damping agent,
The following general formula [I]:

(In the general formula [I], X is at least one substituent selected from the group consisting of an alkyl group, an alkylol group, and a halogen atom, s is 0 to 2, t is 1 or 2, n Is 5-200.)
The present invention provides a vibration-damping material composition, which is a polyvinylphenol-based resin having a repeating unit represented by the following formula:

According to the present invention,
A vibration damping material composition comprising a vibration damping agent and an inorganic filler and / or an organic filler mixed with an organic polymer matrix material,
The vibration damping agent,
The following general formula [I];

(In the general formula [I], X is at least one substituent selected from the group consisting of an alkyl group, an alkylol group, and a halogen atom, s is 0 to 2, t is 1 or 2, n Is 5-200.)
The present invention provides a vibration-damping material composition, which is a polyvinylphenol-based resin having a repeating unit represented by the following formula:

The present invention employs a constitution comprising (a) the organic polymer matrix and (b) a polyvinylphenol-based vibration damping agent as described above, so that the maximum loss elastic modulus (E '') is large and the E '' is large. It is possible to provide a vibration damping material composition having a temperature range giving> 10 ⁸ Pa in a wide range from room temperature to high temperature. Further, by adopting a constitution comprising (a) an organic polymer matrix, (b) a vibration damping agent, and (c) an inorganic filler / organic filler, a vibration damper having a high loss coefficient η in a wide temperature range. A material composition can be provided. Further, according to the present invention, it is also possible to provide a vibration damping material composition in which both the maximum loss elastic modulus (E ″) and the loss coefficient η are improved, and when a conventionally known vibration damping agent is used. It has a remarkably remarkable effect in comparison.

  A first aspect of the present invention relates to a vibration damping material composition containing an organic polymer matrix material and a polyvinylphenol-based resin represented by the general formula [I] as a vibration damping agent. The present invention relates to a vibration damping material composition containing 1) an organic polymer matrix material, (2) a polyvinylphenol-based resin represented by the general formula [I] as a vibration damping agent, and (3) an inorganic filler and / or an organic filler. However, preferred embodiments include those described in the following 1) to 13).

1) The organic polymer matrix material is an acrylic rubber and / or
The above-described vibration damping material composition, which is an acrylate-methacrylate resin.
2) The organic polymer matrix material is polylactic acid resin or polylactic acid.
The above vibration damping material composition, which is a mixture of a resin and an acrylic rubber.
3) The organic polymer matrix material is a polybutylene succinate resin
The above-mentioned vibration damping material composition, which is a mixture of a fat or a polybutylene succinate resin with an acrylic rubber and / or a polylactic acid resin.
4) The organic polymer matrix material contains 10 to 40% of acrylic rubber.
The above-mentioned vibration damping material composition comprising 90 to 60% of a polylactic acid resin.
5) The form of the organic polymer matrix material is an aqueous emulsion.
The vibration damping material composition described above.
6) The vibration damping material composition is used as a master batch,
The above damping material composition, which is diluted with an organic polymer different from the organic polymer of the composition.
7) The polyvinylphenol resin is a polyparavinylphenol resin
The above-mentioned vibration damping material composition which is a fat.
8) The weight average molecular weight of the polyvinyl phenol resin is 700 to 50,
000.
9) The organic filler is sorbitol and / or fluoropolyolefin.
The vibration damping material composition described above.
10) The inorganic filler comprises a basic inorganic filler and an acidic inorganic filler.
The above-described vibration damping material composition, which is at least one inorganic compound selected from the group.
11) The mixing ratio of (a) the vibration damping agent and (b) the inorganic filler and / or the organic filler is (a) :( b) = 1: 0.1 to 1: 5 on a weight basis.
The vibration damping material composition described above.
12) The organic polymer matrix material is an acrylic rubber and / or
The vibration damping material, which is a polylactic acid resin, wherein the matrix material contains 5 to 60% by weight of a polyvinylphenol-based polymer as a vibration damping agent.
Composition.
13) The organic polymer matrix material is an acrylic rubber and / or
Polylactic acid resin, wherein the matrix material is polylactic acid as a vibration damping agent.
5 to 60% by weight of vinylphenol compound, 1 to 20% by weight of sorbitol and / or fluoropolyethylene and 1 to 5% of mica
The above-mentioned vibration damping material composition containing 0% by weight.

Hereinafter, the present invention will be described specifically.
The organic polymer which is useful as a component of the vibration damping material of the present invention and functions as a matrix of a vibration damping agent, has a predetermined molecular weight, a melting point, and a polar side chain, particularly, It is not limited, and specifically, polyurethane resins including acrylic rubber, butyl rubber, chloroprene, SBR (styrene butadiene rubber), thermoplastic elastomer (ethylene propylene rubber), polylactic acid resin, polybutylene succinate resin, Acrylate resin, epoxy resin, polycarbonate resin, polyester resin, polyether resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride polymer, ethylene-methacrylate copolymer, acrylonitrile-styrene copolymer, Acrylonitrile butadiene Styrene copolymers, may be mentioned chlorinated polyethylene, chlorinated polypropylene, an organic polymer such as chlorinated polyolefins such as chlorinated polybutylene. These can be arbitrarily selected and used according to various uses of the vibration damping material, but have a polar group capable of interacting with the vibration damping agent and are effective for environmental protection. Is preferred. Examples of such organic polymers include acrylic rubber, ethylene-acrylic acid copolymer, acrylate-methacrylate resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, polycarbonate resin, polylactic acid resin, and polybutylene succinate resin. And the like. However, particularly preferable organic polymers for the vibration damping material composition according to the present invention are acrylate-methacrylate resin, acrylic rubber, polylactic acid resin, polybutylene succinate resin, acrylic rubber and polylactic acid. A mixture of a resin, a mixture of a polylactic acid and a polybutylene succinate resin, and a mixture of an acrylic rubber and a polybutylene succinate resin.

  Acrylic rubber is a rubber-like elastic body obtained by polymerization of an acrylate ester or copolymerization based on it. As the acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate and the like are used, and as the monomer to be copolymerized, methyl vinyl ketone, acrylic acid, acrylonitrile, butadiene, methyl methacrylate and the like are used. Can be

In addition, polylactic acid resin is usually produced by subjecting lactic acid oligomer obtained by dehydration polycondensation of lactic acid to lactide obtained by further depolymerization for ring-opening polymerization, and is molded and processed by various methods. It is useful for environmental protection because of its excellent performance.
As such a polylactic acid resin, those having a weight average molecular weight of 200,000 to 1,000,000, preferably 300,000 to 800,000 can be employed, and those having a melting point of 150 ° C or more are suitable. The polylactic acid resin containing 10 to 50% by weight of polysaccharides such as cellulose and starch and other additives is particularly preferable from the viewpoint of moldability.

  As the polyurethane resin, a resin having a urethane bond -NHCOO- in a main chain repeating unit and usually obtained by a polyaddition reaction between an organic diisocyanate and a polymer diol can be used. As the organic diisocyanate, raw materials generally used for the production of polyurethanes such as 4,4′-diphenylmethane diisocyanate, p-phenylenediisocyanate, tolylene diisocyanate, and 4,4′-cyclohexylmethane isocyanate can be used. No. The polymer diol and the polymer triol are not particularly limited, but a polyether type such as polyoxypropylene glycol and polyoxypropylene-polyoxyethylene glycol can be used. The polyurethane resin preferable as the organic polymer matrix material contains a high molecular weight diol having an average molecular weight of 500 to 10,000, particularly 1,000 to 7,000.

  As the organic polymer matrix of the vibration damping material according to the present invention, among the various polymers as described above, acrylate-methyl methacrylate resin, acrylic rubber, polylactic acid resin, or acrylic rubber and polylactic acid resin, polylactic acid And a mixture of polybutylene succinate resin and polybutylene succinate resin. Among these, polylactic acid resin or a mixture of acrylic rubber and polylactic acid resin can be mentioned. The mixing ratio with B) may be in the range of (A) :( B) = 10 to 90:90 to 10, preferably 15 to 70:85 to 30 on a weight basis.

  As the organic polymer matrix, a resin emulsion or a material obtained via a resin emulsion can also be used. The resin emulsion is, for example, in the form of being dispersed or emulsified using water or another solvent, an aqueous emulsion obtained using water is preferable from the viewpoint of environmental conservation, and its operation is simple and easy in its preparation. In addition, a uniform quality coating film can be obtained. The content of the solid content of the resin emulsion can be arbitrarily adjusted, but is preferably 20 to 80% by weight, particularly preferably 35 to 65% by weight. Further, the average particle size of the resin in the resin emulsion is preferably in the range of 0.01 to 50 μm, particularly 0.1 to 10 μm.

When the vibration damping material composition is used as a sheet-shaped molded body, the organic polymer matrix has a molding stabilizing effect on the sheet molded body, and also functions as a diluent for the masterbatch of the vibration damping agent. The organic polymer is required to have such qualities as a matrix, and the organic polymer can satisfy this.

Next, a vibration damping agent that is a component constituting the vibration damping material composition according to the present invention,
The following general formula [I]
Is a polyvinylphenol-based resin having a repeating unit represented by the formula:
Such a polyvinylphenol-based resin has specificity in being a resin containing the repeating unit, and includes both a polyvinylphenol homopolymer resin and a polyvinylphenol copolymer resin.

  In the general formula [I], X is at least one substituent selected from the group consisting of an alkyl group, an alkylol group and a halogen atom, and s is an average substitution rate and is an integer of 0 to 2. The alkyl group and the alkylol group each preferably have 1 to 3 carbon atoms. Examples of the halogen atom include bromine, chlorine and fluorine, and among them, bromine is preferable. Also, t indicates the number of hydroxyl groups per unit, and is 1 or 2, preferably 1. n is 5 to 200, preferably 10 to 160, and an optimum range, that is, a material having an optimum molecular weight can be selected according to the use of the damping material which is useful up to a polymer.

  The molecular weight of the polyvinyl phenol resin as the vibration damping agent of the vibration damping material composition according to the present invention is preferably from 700 to 50,000, more preferably from 1,500 to 30,000, weight average molecular weight. If the average molecular weight does not reach 1,500, sufficient vibration damping action cannot be obtained, while if it exceeds 50,000, the interaction with the organic polymer matrix may be reduced.

  The polyvinyl phenol copolymer resin contains a copolymer component, and as copolymerizable monomers, vinyl carboxylate (vinyl acetate, vinyl propionate, etc.); unsaturated carboxylate ((meth) acrylic acid) Methyl, ethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, diethyl maleate, dimethyl itaconate, etc.); aromatic vinyl (styrene, α -Methylstyrene and the like), olefins (ethylene, propylene, butadiene, isoprene and the like); methyl vinyl ether, isobutyl vinyl ether, cetyl vinyl ether, maleic acid, (meth) acrylic acid, acid phosphoxyethyl (meth) acrylate, styrene sulfonic acid, Vinyl alcohol Le, allyl glycidyl ether, it may be used at least one monomer selected from the group consisting of glycidyl (meth) acrylate and the like. Preferred copolymerizable components include acrylic acid monomers, methacrylic acid monomers, styrene and the like.

Examples of the acrylate monomer include alkyl acrylates, for example, methyl acrylate and ethyl acrylate, and examples of the methacrylate monomer include 2-hydroxyethyl methacrylate. The content of the vinylphenol component in all monomers is 30 to 6
0 mol% is preferred. The polyvinylphenol-based resin may be any resin having a linear or branched molecular structure.

Particularly suitable polyvinyl phenol copolymer resin for the vibration damping material composition according to the present invention can be represented by the general formula [II].
Preferred specific examples of the polyvinylphenol copolymer resin include:
The following general formula [II]

Can be represented by

In the general formula [II], the repeating unit is the same as that in the general formula [I], and A is a polymerizable monomer;
The following formula (1) or (2):
Or
Is represented by m is 1 to 200, and particularly preferably 5 to 100.

Thus, a polyparavinylphenol-based resin having a repeating unit represented by the general formula [I] or [II] and having a remarkable vibration damping action, wherein a vinyl group is bonded to the hydroxyl group at the 4-position, Brominated polyparavinylphenol-based resins and the like can be exemplified.
Commercial products of such polyparavinylphenol-based resins include Markarinka MS-1P, MS-2P, MS-3P, MS-4P, MH-2P, MB (manufactured by Maruzen Petrochemical Co., Ltd.) and the like.
Such a polyvinyl phenol-based resin exhibits a remarkably remarkable vibration damping effect in a wide temperature range as a vibration damping agent, can be supplied at low cost, and greatly contributes to industry.

  Such a vibration damping agent can be employed in a range of 5 to 70% by weight, preferably 10 to 55% by weight, more preferably 15 to 50% by weight based on the total weight of the vibration damping material composition. If the content of the vibration damping agent is less than 5% by weight, the vibration damping effect cannot be obtained. On the other hand, if it exceeds 70% by weight, there is a possibility that the phase separation from the organic polymer matrix material may be adversely affected.

  In addition, as the vibration damping material composition according to the present invention, a masterbatch containing a high concentration of a vibration damping agent may be prepared and diluted to prepare a masterbatch. In this case, as the base polymer, those having a polar group as described above can be used, and as the resin for dilution, other resins selected according to the application, such as a polyolefin having no polar group, etc. Can also be used.

  Next, the inorganic filler and the organic filler used as constituents of the vibration damping material composition of the present invention are inorganic fillers, carbon-based fillers and organic fillers as long as the filler has a strong interaction with the organic polymer matrix. Any of the fillers can be selected.

The inorganic filler, calcium carbonate, talc, magnesia, saponite, smectite, montmorillonite, vermiculite, Sottoraito, mica, stainless steel powder, tourmaline, BaTiO _3, SiO _2, such as _{PbTiZrO 3, Al 2 O 3,} MgO, Na 2 Layered compounds containing O 2 and the like, talc, calcium carbonate, natural zeolites, synthetic zeolites, mesoporous zeolites, flaky silica, and the like are useful. Examples of the carbon-based filler include Ketjen black carbon, seam carbon, and flake graphite.

In particular, as a preferable inorganic filler, when the organic polymer or the organic polymer damping agent mixture system is acidic, a basic inorganic filler is preferable. Examples of the basic inorganic filler include TiO ₂ , MgO, CaO, and talc. Further, a layered silicate clay mineral can be used as the acidic inorganic filler. As the layered silicate clay mineral, a 2: 1 type mineral is preferable. In particular, one having a relatively large bottom interval, that is, a unit structure thickness and a period that is relatively large in a direction perpendicular to the layer surface, for example, about 14 to 15 ° or more Can be used. Specifically, besides mica, smectite, montmorillonite, saponite, vermiculite, talc and the like or a mixture thereof are useful.

  As the organic filler, dibenzylidene sorbitol, tetrafluoropolyethylene, sulfenamides, benzothiazoles, guanidines, gerol D, cellulose powder, nonwoven fabric, wood chips, sugar, paper, cellulose, FRP, or the like can be used. it can.

Examples of the sulfenamides include N-cyclohexyl-2-benzothiazolylsulfenamide, Nt-butyl-2-benzothiazolylsulfenamide, N, N′-oxydiethylene-2-benzothiazolylsulfone Benzothiazolylsulfenamides such as phenamide, N, N′-dicyclohexyl-2-benzothiazolylsulfenamide and N, N-diisopropyl-2-benzothiazolylsulfenamide. Particularly preferred benzothiazolylsulfenamides are N, N'-dicyclohexyl-2-benzothiazolylsulfenamide.

Examples of benzothiazoles include 2- (N, N-diethylthiocarbamoylthio) benzothiazole, 2- (4′-morpholinodithio) benzothiazole, and the like.
Examples of benzotriazoles include 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-. Chlorobenzotriazole and the like can be exemplified.
Further, examples of guanidines include those containing a basic nitrogen such as 1,3-diphenylguanidine and di-o-tolylguanidine.

By using the inorganic filler and the organic filler together, the temperature range in which a high level of loss modulus (E ″) can be remarkably expanded.
Such inorganic fillers and organic fillers are preferably used in the form of fine particles, particularly flakes or fibers, and those having an average particle size of 0.1 to 200 μm, particularly 40 to 100 μm, contribute to vibration absorption and sound absorption. But big.
In particular, by replacing a part of the blending amount of the phenolic compound with an organic filler and combining the phenolic compound, the organic filler and the inorganic filler, a high loss modulus (E) can be obtained over a wide range of temperatures, especially in a high temperature region. '').

The compounding amount of the inorganic filler is 2 to 80% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight based on the total weight of the vibration damping material composition. If the compounding amount does not reach 2% by weight, sufficient improvement in vibration absorption performance cannot be seen, while if it exceeds 80% by weight, there are difficulties such as strength reduction due to phase separation, and sufficient material strength is maintained. I can't.
The compounding amount of the organic filler is preferably 2 to 50% by weight, particularly preferably 4 to 30% by weight.

In the vibration damping material composition according to the present invention, the mixing ratio of the organic polymer matrix material (a), the phenolic compound (b) and the inorganic filler and / or the organic filler (c) is as follows: component (a); 50% by weight, preferably 10-40% by weight, component (b); 5-60% by weight, preferably 10-40% by weight, and component (c); 2-70% by weight, preferably 10-60% by weight Can be adopted.
Such an inorganic filler and an organic filler can be used as a master batch-formed resin composition with a base resin in addition to the vibration damping agent, like the vibration damping agent.

Further, in the vibration damping material composition according to the present invention, another organic polymer can be blended with the base resin used as the organic polymer according to a desired purpose. For example, a material different from the base resin may be selected, but melamine resin, phenol resin, polyethylene terephthalate, polycarbonate, polyolefin and the like can be used.
Furthermore, the vibration damping material composition according to the present invention may be blended with other additives such as a lubricant, an antioxidant, and a foaming agent.

  The vibration damping material composition according to the present invention can be obtained in the form of fibrous, granular, powder, or the like, but can be used in any form depending on the machine, equipment, building, or the like that requires vibration damping. In particular, it is preferable to use in the form of a sheet-shaped molded body, and the thickness of the sheet-shaped molded body can be arbitrarily determined according to various applications and required performance levels. In particular, it is preferable to use a material having a range of 1 to 4 mm. The vibration damping material composition according to the present invention can also be provided in the form of a paint. For example, it is possible to apply a foamed structure and a complicated structure, or to apply a laminated structure to individual laminated sheet bodies, and sandwich a vibration damping material between the laminated structures. The object includes various structures, for example, buildings, machinery, transportation devices, and any other objects that need damping.

  Although the method for producing the vibration damping material composition according to the present invention as described above is not particularly limited, for example, the following production method can be employed for a sheet-like molded product and a paint. Specific production conditions may be selected according to the use of the raw materials and the damping materials.

(1) Sheet-shaped molded body
Each particle of (a) organic polymer and (b) vibration damping agent or each particle of (a) organic polymer, (b) vibration damping agent and (c) organic filler and / or inorganic filler After kneading at a predetermined ratio at a temperature equal to or higher than ordinary temperature, the mixture is subjected to conditions necessary for pressure bonding, for example, at 60 to 300 ° C, preferably 100 to 200 ° C, and 130 to 300 kgf / cm ² , preferably 100 to 250 kgf. Pressing / stretching and molding under temperature / pressure conditions of / cm ² .

(2) Paint
(a) An emulsion of an organic polymer is dispersed and mixed with (b) a vibration damping agent, or (a) an emulsion of an organic polymer is mixed with (b) a vibration damping agent and (c) an organic filler and / or an inorganic filler. A paint containing the mixture obtained by dispersion mixing is prepared. What is necessary is just to adjust the mixing ratio of each raw material so that the said damping material composition may be obtained.
The sheet-shaped molded body can be applied to an application surface requiring a vibration damping effect, for example, by sandwiching it between one or more layers of various kinds of laminated boards or by pressing it to the surface.
Further, the form of the vibration damping material composition according to the present invention can be provided as a liquid material such as a paint, and is applied to an interlayer or a surface of a laminate to form a coating film, thereby performing a vibration damping action. be able to.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited at all by the examples and the like.
In addition, a dynamic viscoelasticity measurement test device (DVA-200S manufactured by IT Measurement Control Co., Ltd.) was used to measure the loss elastic modulus (E ″) of the vibration damping material compositions obtained in the examples and comparative examples. . The measurement was performed in a tensile mode between -50 and 100 ° C. at a frequency of 50 Hz, a heating rate of 5 ° C./min, and a dynamic strain of 0.1%. The size of the sample was about 20 mm × 5 mm × 1 mm.

The loss coefficient η was measured by a central excitation method according to JIS G 0602; 1993 shown in FIG. Figure shows the measurement sample A was adhered to a vibration damping material sheet A ₁ in the cold-rolled steel plate substrate A _2. B indicates an impedance head, C indicates a vibrator, and D indicates an apparatus for measuring vibration damping characteristics comprising an analyzer (Fourier transform using modal analysis software, and a loss coefficient η is obtained from a resonance peak by a half-value width method). Using a cold-rolled steel plate having a substrate size of 200 mml x 10 mmw x 0.8 mmt, a vibration damping material sample was adhered and measured at an area density of ² kg / m2.

Examples 1 to 7
100 parts by weight of an acrylic rubber was used as an organic polymer matrix material, and various poly-4-vinylphenol resins (polyparavinylphenol resins) shown in Table 1 (“Marcalinker M” manufactured by Maruzen Petrochemical Co., Ltd.) were used as damping agents. Series) are kneaded at the ratios shown in the table, and then the mixture is pressurized to 200 kgf / cm ² at 180 ° C. by a hot press machine to prepare a vibration-damping material composition formed into a sheet having a thickness of 1 mm. did. The evaluation results are shown in the same table.

Examples 8 and 9
As the organic polymer matrix material, a mixture of the same amounts of polylactic acid and polybutylene succinate was used, and as a vibration damping agent, a poly4-vinylphenol resin shown in Table 1 (“Marukalinker M” series manufactured by Maruzen Petrochemical Co., Ltd.) ) Was kneaded at the ratios shown in the same table, and the mixture was pressurized to 180 kgf / cm ² at 180 ° C. using a hot press machine to prepare a vibration-damping material composition formed into a sheet having a thickness of 1 mm.

Comparative Examples 1-4
Acrylic rubber, polylactic acid and polybutylene succinate are used as the organic polymer matrix, and 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 4,4′-thiobis (3-methyl) are used as vibration damping agents. −6-t-butylphenol) was kneaded at a ratio shown in Table 2 to prepare a vibration damping material composition. Table 2 shows the evaluation results of the respective vibration damping material compositions prepared using polylactic acid and polybutylene succinate alone.

Note 1) Acrylic rubber AR32 manufactured by Zeon Corporation
Note 2) Shimadzu polylactic acid resin Lacty 5000
Note 3) Polybutylene succinate Vionore 1001 manufactured by Showa Polymer Co., Ltd.
Note 4) PH1; poly 4-vinylphenol resin (weight average molecular weight 2100)
(Marukalinker MS-1P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 5) PH2: Poly 4-vinylphenol resin (weight average molecular weight 4800)
(Marcalinker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 6) PH3; poly4-vinylphenol resin (weight average molecular weight 9300)
(Marukalinker MS-4P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 7) PH4: Poly 4-vinylphenol resin (weight average molecular weight 20,900)
(Marukalinker MH-2P manufactured by Maruzen Petrochemical Co., Ltd.)

Note 1) Acrylic rubber AR32 manufactured by Zeon Corporation
Note 2) Shimadzu polylactic acid resin Lacty 5000
Note 3) Polybutylene succinate Vionore 1001 manufactured by Showa Polymer Co., Ltd.
Note 8) PH5; 22 'methylenebis (4-methyl-6-tbutylphenol)
(Nocrack NS6 manufactured by Ouchi Shinko Chemical Co., Ltd.)
Note 9) PH6; 44 'thiobis (3-methyl-6-tbutylphenol)
(Nocrack 300 manufactured by Ouchi Shinko Chemical Co., Ltd.)

Examples 11 to 14
Acrylic rubber and polypropylene were mixed in the proportions shown in Table 3 as the organic polymer matrix material, and the poly-4-vinylphenol-based resins shown in the same table were mixed at the weight proportions shown in the same table as vibration damping agents. Thereafter, the mixture was pressurized by a hot press at 140 to 180 ° C. at 100 to 200 kgf / cm ^{2 for} 20 minutes to prepare a vibration-damping material composition formed into a sheet.
In order to observe the vibration damping performance by the above evaluation method, a temperature range where the loss coefficient (η) gives 0.08 or more was measured. Table 3 shows the evaluation results.

Note 1) Acrylic rubber AR32 manufactured by Zeon Corporation
Note 2) Idemitsu Petrochemical Co., Ltd. random polypropylene Note 3) PVPH1; poly 4-vinylphenol resin (weight average molecular weight 2100)
(Marukalinker MS-1P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 4) PVPH2: Poly 4-vinylphenol resin (weight average molecular weight 4800)
(Marcalinker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 5) PVPH3; poly 4-vinylphenol resin (weight average molecular weight 9300)
(Marukalinker MS-4P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 6) PVPH4; poly 4-vinylphenol resin (weight average molecular weight 20,900)
(Marukalinker MH-2P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 7) OF2: dibenzylidene sorbitol (manufactured by Ciba Specialty Chemical Co., Ltd.)
IRGACLEAR D)
Note 8) IF1; Mica (Kuraray Szolite Mica 200HK)
Note 9) IF3; carbon (Cabot 300)

Examples 15 to 22
An acrylic emulsion, a vinyl acetate emulsion, and a polyurethane emulsion are mixed with a poly4-vinylphenol resin and a copolymer thereof in the proportions shown in Table 4, and further a stabilizer, a dispersant, an antifoaming agent, a filler, and a viscosity control. The agent and water were added. Further, an inorganic filler was added to obtain a paint.
A predetermined amount of the prepared coating material was applied on a substrate, air-dried, and then heat-treated at 100 to 200 ° C. The evaluation results are shown in the same table.

Note 1) High pressure gas styrene acrylic emulsion P873
* 2) High pressure gas methyl methacrylate acrylic emulsion P781
Note 3) Showa Polymer Co., Ltd. ethylene vinyl acetate emulsion EVAP20
* 4) Urethane emulsion F8598E manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Note 5) PVPH1: Poly 4-vinylphenol resin (weight average molecular weight 2100)
(Marukalinker MS-1P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 6) PVPH2; poly 4-vinylphenol resin (weight average molecular weight 4800)
(Marcalinker MS-2P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 7) PVPH3; poly 4-vinylphenol resin (weight average molecular weight 9300)
(Marukalinker MS-4P manufactured by Maruzen Petrochemical Co., Ltd.)
Note 8) PH9; 2,2'-bis (4-hydroxy-3-methylphenyl) propane
Tokyo Chemical Industry B1567
Note 9) PVPH8: Poly 4-vinylphenol-methyl methacrylate-copolymer resin (weight average molecular weight 5000) (Marukalinker CM manufactured by Maruzen Petrochemical Co., Ltd.)
M)
Note 10) PVPH9: poly 4-vinylphenol-2 hydroxyethyl-methacrylate copolymer resin (weight average molecular weight 1400) (Marukalinker CHM manufactured by Maruzen Petrochemical Co., Ltd.)
Note 11) PH10: Poly 4-vinylphenol-styrene-copolymer resin (weight average molecular weight: 5000) (Marukalinker CST manufactured by Maruzen Petrochemical Co.)
Note 12) OF1: an aqueous solution containing 20% of a stabilizer, dispersant, defoaming agent, viscosity modifier Note 13) OF2; N, N'-dicyclohexylbenzothiazyl-2-sulfenamide Note 14) IF1; Mica ( Kuraray Szolite Mica 200HK)
Note 15) IF2; talc (SSS talc manufactured by Nippon Taishi Smelting Co., Ltd.)

Comparative Example 5
As a vibration damping agent, a hindered phenol compound 2,2′-methylenebis (4-methyl-6-t-butylphenol) is used in place of the poly-4-vinylphenol resin, and the composition of the vibration damping material is the same under the same production conditions. Was prepared. Table 5 shows the evaluation results.

Comparative Example 6
The same as Comparative Example 1 except that a hindered phenol compound 4,4′-thiobis (3-methyl-6-t-butylphenol) was used as the vibration damping agent instead of the poly-4-vinylphenol resin. And a vibration damping material composition were prepared under the same manufacturing conditions. Table 5 shows the evaluation results.

Note 1) Acrylic rubber AR32 manufactured by Zeon Corporation
Note 2) PH101; 2,2'-methylenebis (4-methyl-6-t-butylphenol)
Ouchi Shinko Chemical Nocrack NS6
Note 3) Mica (Kuraray Szolite Mica 200HK)
Note 14) IF1: Mica (Kuraray Szolite Mica 200HK)

  The present invention provides a vibration damping material composition obtained by blending a vibration damping agent, an inorganic filler and / or an organic filler with an organic polymer matrix material. The composition has a large loss elastic modulus and loss coefficient in a high-temperature region, and a wide usable temperature range in a high-temperature region, so that it can be used in a wide range of regions, for example, automobiles, buildings, various industrial machinery, home appliances, As a material for medical equipment and the like, it can be used for a wearable material and other laminated materials that can attenuate vibration and sound, and greatly contributes to industry.

This is an evaluation device for the loss coefficient (η) of the damping material composition.

Explanation of reference numerals

A: Test piece A ₁ : Sample (damping material sheet)
A ₂ : Base material B: Impedance head C: Exciter D: Transfer function analyzer (PC for FFT analysis)

Claims (10)

A vibration damping material composition obtained by blending a vibration damping agent with an organic polymer matrix material,
The vibration damping agent,
The following general formula [I];
(In the general formula [I], X is at least one substituent selected from the group consisting of an alkyl group, an alkylol group, and a halogen atom, s is 0 to 2, t is 1 or 2, n Is 5-200.)
A vibration damping material composition, which is a polyvinylphenol resin having a repeating unit represented by the following formula: A vibration damping material composition comprising a vibration damping agent and an inorganic filler and / or an organic filler mixed with an organic polymer matrix material,
The vibration damping agent,
The following general formula [I];
(In the general formula [I], X is at least one substituent selected from the group consisting of an alkyl group, an alkylol group, and a halogen atom, s is 0 to 2, t is 1 or 2, n Is 5-200.)
A vibration damping material composition, which is a polyvinylphenol resin having a repeating unit represented by the following formula: The organic polymer matrix material, vinyl acetate resin, ethylene-vinyl acetate resin, epoxy resin, alkyd resin, polyester resin, polyurethane resin, polycarbonate resin, polylactic acid resin, polybutylene succinate resin, Polyether resin, ethylene-methacrylate resin, acrylate-methacrylate resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene resin, acrylic rubber, butyl rubber, halogenated polyolefin, polyethylene and polypropylene 3. The vibration damping material composition according to claim 1, which is at least one polymer compound selected from the group. The vibration damping material composition according to claim 1 or 2, wherein the vibration damping agent is a poly4-vinylphenol homopolymer resin having a weight average molecular weight of 700 to 50,000. The vibration damping agent has the following general formula [II]
(In the general formula [II], X is at least one substituent selected from the group consisting of an alkyl group, an alkylol group, and a halogen atom, s is 0 to 2, t is 1 or 2, n Is 5-200, and A is
Or
And m is 1 to 20. )
The vibration damping material composition according to claim 1 or 2, which is a polyvinylphenol copolymer resin having a repeating unit represented by the following formula: 3. The vibration damping material composition according to claim 1, wherein the compounding amount of the vibration damping agent is 5 to 70% by weight based on the total weight of the vibration damping material composition. 4. The vibration damping material composition according to claim 2, wherein the amount of the inorganic filler is 2 to 80% by weight based on the total weight of the vibration damping material composition. The vibration damping material composition according to claim 2, wherein the compounding amount of the organic filler is 1 to 30% by weight based on the total weight of the vibration damping material composition. The vibration damping material composition according to claim 1 or 2, wherein the vibration damping material composition is a sheet-like molded body having a thickness of 0.05 to 7 mm. The vibration damping material composition according to claim 1 or 2, wherein the vibration damping material composition is a coating film applied to a structure.