JP2004149767A - Vibration-damping material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vibration-damping material composition having a large loss tangent tanδ and a loss factor η and a wide temperature range for using the same. <P>SOLUTION: The vibration-damping material composition comprises an organic polymer matrix material containing a vibration-damping imparting material, an inorganic filler and/or an organic filler. The vibration-damping imparting material is a less hindered type having little steric hindrance and a phenol-based compound having a chemical structure which has no ≥4C branched hydrocarbon group on both adjacent positions of a hydroxyl group. <P>COPYRIGHT: (C)2004,JPO

Description

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

  In the industrialized society in recent years, as the need for energy saving and low environmental load has increased from the viewpoint of global environmental protection, there has been a strong demand for weight reduction of vibration damping materials and sound insulation materials.

  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 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, the 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. As a result, not only the number of interactions between the damping agent and the polymer decreases, but also at high temperatures, the dissociation of the interactions easily occurs. Therefore, a high loss tangent (tan δ) is required as a performance required for vibration damping. Alternatively, there is a disadvantage that the usable temperature range showing the loss coefficient (η) is 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

  Therefore, an object of the present invention is to provide a vibration-damping material having a more excellent vibration-damping function as compared with a conventionally proposed vibration-damping material using a phenolic compound, that is, a maximum loss tangent (tan δ) and a loss coefficient (tanδ). It is an object of the present invention to provide a vibration damping material composition having a high η), a wide usable temperature range for each of them, and a durability capable of maintaining the vibration damping function at a high level for a long period of time.

  Thus, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as compared with conventional phenolic compounds, specific phenolic compounds having a stronger interaction with a vibration damping material matrix composed of an organic polymer. A damping material composition obtained by containing a compound exhibits a high loss tangent (tan δ) and a loss coefficient (η) in a wide temperature range and provides a damping material composition having a wide usable temperature range. They have found that they can do this 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):

(Where
A represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom, the chain hydrocarbon group having an aromatic group, or an alicyclic carbon group having 5 to 8 carbon atoms. A hydrogen group,
B is a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom;
A and B may be the same or different from each other,
R ₁ , R ₂ and R ₃ are each a hydrocarbon group having 3 or less carbon atoms, an alkylol group or an aldehyde group, which may be the same or different, and p, q and r are each an integer of 0 to 3 And may be the same or different from each other,
X is a halogen atom, s, t and u are each 0 or 1, and may be the same or different from each other;
x, y and z are each an integer of 1 to 3 and may be the same or different from each other, and n is 0 to 200. )
And a damping material composition characterized by being a phenolic compound represented by the formula:

According to the present invention,
A vibration damping material composition, wherein the organic polymer matrix material comprises a vibration damping agent and an inorganic filler and / or an organic filler,
The vibration damping agent,
The following general formula (I):

(Where
A represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom, the chain hydrocarbon group having an aromatic group, or an alicyclic carbon group having 5 to 8 carbon atoms. A hydrogen group,
B is a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom;
A and B may be the same or different from each other,
R ₁ , R ₂ and R ₃ are each a hydrocarbon group having 3 or less carbon atoms, an alkylol group or an aldehyde group, which may be the same or different, and p, q and r are each an integer of 0 to 3 And may be the same or different from each other,
X is a halogen atom, s, t and u are each 0 or 1, and may be the same or different from each other;
x, y and z are each an integer of 1 to 3 and may be the same or different from each other, and n is 0 to 200. )
And a damping material composition characterized by being a phenolic compound represented by the formula:

  The first aspect of the present invention relates to a vibration damping material composition containing an organic polymer matrix material and a phenolic compound represented by the general formula (I) as a vibration damping agent. 1) An organic polymer matrix material, (2) a vibration damping material composition containing a phenolic compound represented by the general formula (I) as a vibration damping agent and (3) an inorganic filler and / or an organic filler. However, preferred embodiments further include those described in the following 1) to 10).

1) The organic polymer matrix material is 10 to 40% of acrylic rubber
And the polylactic acid resin is 90 to 60%.
2) The form of the organic polymer matrix material is an aqueous emulsion.
The above-mentioned vibration damping material composition.
3) The vibration damping material composition is used as a master batch,
Diluted with an organic polymer different from the organic polymer of the filler composition
The vibration damping material composition.
4) The vibration damping agent has a methyl group at a position adjacent to one side of the hydroxyl group.
The vibration damping material composition is a bisphenol compound.
5) The vibration damping material, wherein the phenolic compound has a melting point of 100 ° C. or more.
Composition.
6) The vibration damping material, wherein the phenolic compound has a molecular weight of 200 or more.
Composition.
7) The organic filler is sorbitol and / or fluoropolyole.
The above-mentioned vibration damping material composition which is a fin.
8) The vibration damping agent (a) and the inorganic filler and / or the organic filler
The blending ratio of (b) is (a) :( b) = 1: 0.1 to 1: 5.
The vibration damping material composition.
9) The organic polymer matrix material is an acrylic rubber and / or
Is a polylactic acid resin, and the matrix material serves as a vibration damping agent,
2,2'-methylenebis (4-methylphenol), 2,2'-bi
(4-hydroxy-3-methylphenyl) propane and 1,1 ′
From the group consisting of -bis (4-hydroxyphenyl) cyclohexane
5 to 60% by weight of at least one selected phenolic compound
The above-mentioned vibration damping material composition comprising:
10) The organic polymer matrix material is an acrylic rubber and / or
Is a polylactic acid resin, and the matrix material serves as a vibration damping agent,
2,2'-methylenebis (4-methylphenol), 2,2'-bi
(4-hydroxy-3-methylphenyl) propane and 1,1 ′
From the group consisting of -bis (4-hydroxyphenyl) cyclohexane
5 to 60% by weight of at least one phenolic compound selected
Rabbit sorbitol and / or fluoropolyethylene 1-20
% By weight and 1 to 50% by weight of mica
object.

  The present invention employs a constitution comprising (a) the organic polymer matrix and (b) the vibration damping agent as described above, so that the maximum loss tangent tan δ is large and the temperature range giving tan δ> 1 is from normal temperature to high temperature. Vibration damping material compositions having a wide range can be provided. Further, a vibration damping material composition having a high loss coefficient η is provided by adopting a constitution comprising (a) an organic polymer matrix, (b) a vibration damping agent, and (c) an organic filler / inorganic filler. be able to. Further, according to the present invention, it is also possible to provide a vibration damping material composition in which both the maximum loss tangent (tan δ) and the loss coefficient η are improved, as compared with the case where a conventionally known vibration damping agent is used. It has a remarkable effect.

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, Without being limited, specifically, acrylic rubber, butyl rubber, chloroprene, SBR (styrene butadiene rubber), thermoplastic elastomer (ethylene propylene rubber), polylactic acid resin, polyurethane 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 copolymer Polymer, chlorinated poly Styrene, chlorinated polypropylene, and organic polymers 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 an organic polymer include acrylic rubber, ethylene-acrylic acid copolymer, acrylate-methacrylate resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, polycarbonate resin, polylactic acid resin, and the like. However, particularly preferred organic polymers for the vibration damping material composition according to the present invention are acrylate-methacrylate resins, acrylic rubbers, polylactic acid resins or mixtures of acrylic rubbers and polylactic acid resins.

  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 described above, acrylate-methyl methacrylate resin, acrylic rubber, polylactic acid resin, or a mixture of acrylic rubber and polylactic acid resin Among these, a polylactic acid resin or a mixture of an acrylic rubber and a polylactic acid resin can be mentioned, and the mixing ratio of the acrylic rubber (A) and the polylactic acid resin (B) is based on weight, (A) :( B) = 10-90: 90-10, preferably 15-35: 85-65.

  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-like molded body, the organic polymer matrix has a molding stabilizing effect on the sheet molded body, and also functions as a diluent for the master batch 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,
General formula (I)

A phenolic compound represented by
The compounds represented by the general formula (I) include less hindered phenolic compounds having less steric hindrance. By selecting such a less hindered type phenolic compound, the interaction with the organic polymer matrix material remarkably progresses, the maximum loss tangent (tan δ) is higher than that of the hindered type phenolic compound, and It has been found that a wide range of temperature can provide a vibration damping effect.

  The general formula (I) shows that the compound has at least two phenol rings, and also includes a polymer compound in which the phenol rings are connected by the bonding groups represented by A and B. Is disclosed.

  In the formula, A is a short-chain hydrocarbon group which may contain a sulfur atom and / or an oxygen atom, that is, a chain hydrocarbon group having 1 to 3 carbon atoms. The chain hydrocarbon group is a divalent hydrocarbon group, and examples thereof include a methylene group, an ethylene group, a propylene group, and an isopropylene group. Further, those in which an aromatic group is bonded to these hydrocarbon groups, for example, a methylene group in which a phenyl group is bonded

A compound in which an aromatic group having a hydroxyl group is bonded to the hydrocarbon group, for example, a methylene group having a phenol group

Can be mentioned. Further, as A, an alicyclic hydrocarbon group having 5 to 8 carbon atoms, for example, a cyclohexyl group

Can also be mentioned.
In the general formula (I), B is a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom, specifically, a divalent hydrocarbon group such as methylene Group, ethylene group, propylene group or isopropylene group, and A and B may be the same or different from each other.

In the general formula (I), R ₁ , R ₂ and R ₃ are each a hydrocarbon group having 3 or less carbon atoms, an alkylol group or an aldehyde group. Specifically, the hydrocarbon group is a methyl group, An alkyl group selected from an ethyl group, a propyl group, and an isopropyl group, an alkylol group includes, for example, a methylol group and an ethylol group, and an aldehyde group includes, for example, a formyl group. Such R ₁ , R ₂ and R ₃ may be the same or different from each other. Further, p, q and r indicating the number of bonds of R ₁ , R ₂ and R _{3 to} the aromatic ring are each an integer of 0 to 3, and preferably 1 or 2. Such p, q and r may be the same or different from each other.

The bonding position of R ₁ , R ₂ and R _{3 to} the aromatic ring may be arbitrarily determined as long as a reshindered phenolic compound can be realized, but does not occupy both adjacent positions of the hydroxyl group at the same time. Is preferred.

  X represents halogen, and s, t, and u are each 10 or 1, and may be the same or different. Examples of the halogen include chlorine and bromine, and chlorine is preferable.

x, y and z indicate the number of bonds of the hydroxyl group to the aromatic ring, and each is an integer of 1 to 3 and may be the same or different from each other.
N is a repeating unit

Represents the number of repetitions of 0 to 200, and includes a polymer compound. Usually, a compound in which n is 0 to 10 is used, but when it exceeds 10, the function as an organic polymer matrix of the vibration damping material according to the present invention can be exhibited in addition to the function as a vibration damping agent.

Thus, examples of the compound represented by the general formula (I) which is remarkable in damping action are shown below.
2,2'-methylenebis (4-methylphenol);
2,2'-methylenebis (4-ethylphenol);
2,2′-methylenebis (4-propylphenol);
2,2'-methylenebis (4-chlorophenol);
4,4′-methylenebis (2,5-dimethylphenol);
4,4'-methylenebis (2-methyl-5-ethylphenol);
4,4′-methylenebis (4-methyl-5-propylphenol);
2,6-bis (2-hydroxy-5-methylphenyl) -4-methylphenol;
2,2′-bis (4-hydroxy-3-methylphenyl) propane;
1,1′bis (4-hydroxyphenyl) cyclohexane;
α, α ′ (4-hydroxyphenyl) -1,4-diisopropylbenzene;
Bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane;
Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane;
Bis (3-formyl-4-hydroxy-2-methylphenyl) methane;
Bis (4,5-dihydroxy-2-methylphenyl) phenylmethane;
Bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane;
Bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane;
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane;
a, a, a ', a'-tetrakis (4-hydroxyphenyl) -p-xylene;
2,2'-bis [4-hydroxy-3,5-bis (2-hydroxy-5-methylbenzyl) -phenyl] propane

As described above, the above-mentioned phenolic compounds can be mentioned as the vibration damping agent of the vibration damping material composition according to the present invention, and particularly preferred are the following.
2,2'-methylenebis (4-methylphenol);
2,2'-methylenebis (4-ethylphenol);
2,2′-methylenebis (4-propylphenol);
2,2'-methylenebis (4-chlorophenol);
4,4′-methylenebis (2,5-dimethylphenol);
4,4'-methylenebis (2-methyl-5-ethylphenol);
4,4′-methylenebis (4-methyl-5-propylphenol);
2,6-bis (2-hydroxy-5-methylphenyl) -4-methylphenol;
2,2′-bis (4-hydroxy-3-methylphenyl) propane;
1,1′bis (4-hydroxyphenyl) cyclohexane;
α, α '(4-hydroxyphenyl) -1,4-diisopropylbenzene

More preferred phenolic compounds are
2,2'-methylenebis (4-methylphenol);
2,2'-methylenebis (4-chlorophenol);
2,2′-bis (4-hydroxy-3-methylphenyl) propane;
1,1'bis (4-hydroxyphenyl) cyclohexane.

  Such a phenolic compound has a remarkably remarkable vibration damping effect in a wide temperature range as a vibration damping agent, and has a relatively simple chemical structure, without requiring a complicated manufacturing process. Therefore, it can be supplied at low cost and greatly contributes to the industry.

  Such a vibration damping agent can be employed in a range of 5 to 70% by weight, preferably 10 to 60% by weight, and 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 and organic fillers 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 they have strong interaction with the organic polymer matrix. Can be selected.

Examples of the inorganic filler include saponite, smectite, montmorillonite, vermiculite, sotrite, mica, stainless powder, tourmaline, a layered compound containing SiO ₂ such as BaTiO ₃ , PbTiZrO ₃ , Al ₂ O ₃ , MgO, Na ₂ O, 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 and flake graphite.

In particular, when the organic polymer is acidic, a preferable inorganic filler is a basic inorganic filler. 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, montmoroclonite, saponite, vermiculite, etc., or a mixture thereof are useful.

Examples of the organic filler include dibenzylidene sorbitol, tetrafluoropolyethylene, sulfenamides, benzothiazoles, benzotriazoles, guanidines, gelol D, cellulose powder, nonwoven fabric, wood chips, sugar, paper, cellulose, FRP, and the like. Can be used. 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 such an inorganic filler and an organic filler in combination, the temperature range in which a high level of loss coefficient (η) is provided can be significantly expanded.
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. large.

  In particular, by replacing a part of the blending amount of the phenolic compound with the organic filler and combining the phenolic compound, the organic filler and the inorganic filler, a high loss factor (η) can be obtained in a wide temperature range, particularly in a high temperature range. ) Can be achieved.

  The compounding amount of the inorganic filler is 2 to 70% by weight, preferably 20 to 65% by weight based on the total weight of the vibration damping material composition. If the blending amount does not reach 2% by weight, sufficient improvement in vibration absorption performance cannot be seen. On the other hand, if it exceeds 70% by weight, difficulties such as strength reduction due to phase separation occur, and sufficient material strength is maintained. Can not. The compounding amount of the organic filler can be adopted in the range of 1 to 30% by weight, preferably 2 to 20% by weight, particularly 2 to 10% by weight.

  When the vibration damping material composition according to the present invention comprises (a) an organic polymer matrix material, (b) a phenolic compound, and (c) an inorganic filler and an organic filler, the mixing ratio of each component is (A); 5 to 50% by weight, preferably 10 to 30% by weight, component (b); 5 to 60% by weight, preferably 10 to 40% by weight, particularly 5 to 20% by weight, and component (c). 2 to 80% by weight, preferably 10 to 70% by weight.

Such organic and inorganic fillers can be used as a master batch 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, and the object thereof is various structures, for example, buildings, machinery, and any equipment that requires vibration damping such as a transportation device. Include.

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.

  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 normal temperature, the mixture is subjected to conditions necessary for pressure bonding, for example, 60 to 300 ° C, preferably 100 to 200 ° C, 100 to 300 kgf / cm ² , and preferably 150 to 250 kgf /. Press or stretch under temperature and pressure conditions of cm ² to form.
(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.

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.
The loss tangent (tan δ) of the vibration damping material compositions obtained in Examples and Comparative Examples was measured using a dynamic viscoelasticity measurement test device (DVA-200S manufactured by IT Measurement Control Co., Ltd.). 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 the 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). As the substrate A _2, uses a cold-rolled steel sheet of size 200mml × 10mmw × 0.8mmt, the damping material sample was subjected to measurement of attachment loss factor η in areal density of 2 kg / m ² thereto.

Examples 1 to 6
100 parts by weight of an acrylic rubber as an organic polymer matrix material (hereinafter referred to as “polymer matrix”) were mixed with phenolic compounds shown in Table 1 as vibration damping agents in the respective weight ratios shown in the same table. 20 minutes pressurized at 200 kgf / cm ² at 200 ° C. by a hot press to prepare a sheet-like molding processability and damping material composition having a thickness of 1 mm.

  The maximum loss tangent (tan δ) and the temperature region giving tan δ> 1 were measured by the above evaluation method. The evaluation results are shown in Table 1.

Comparative Example 1
All the same raw materials and the same production as in Example 1 except that the hindered phenol-based compound 2,2′-methylenebis (4-methyl-6-t-butylphenol) shown in Table 2 was used as the vibration damping agent. Under the conditions, a vibration damping material composition was obtained. Table 2 shows the evaluation results.

Comparative Example 2
A vibration damping material composition was obtained using the same raw materials and the same manufacturing conditions as in Comparative Example 1 except that no vibration damping agent was used. Table 2 shows the evaluation results.

Comparative Example 3
A vibration damping material composition was obtained using the same raw materials and the same manufacturing conditions as in Comparative Example 2 except that a polylactic acid resin was used instead of the acrylic rubber as the organic polymer. Table 2 shows the evaluation results.

Examples 11 to 18
An acrylic rubber as an organic polymer matrix shown in Table 2 and a phenolic compound as a vibration damping agent, an organic filler and an inorganic filler were blended in the weight ratio shown in the same table to prepare a vibration damping material composition. Table 3 shows the evaluation results.

Example 19
A vibration damping material composition was prepared using the same raw materials and the same conditions as in Example 11 except that a mixture of acrylic rubber 100 and polycarbonate 20 was used instead of acrylic rubber as the organic polymer matrix. Table 4 shows the evaluation results.

Examples 20 to 23
A polystyrene rubber / acrylic rubber or an ethylene-vinyl acetate resin is used as an organic polymer matrix, and a phenol-based vibration damping agent and an inorganic / organic filler shown in Table 4 are mixed in the proportions shown in the same table, respectively, to suppress vibration. A material composition was prepared. Table 4 shows the evaluation results.

Comparative Example 21
The same as Example 11 except that 2,2′-methylenebis (4-methyl-6-t-butylphenol) was used instead of 2,2′-methylenebis (4-methylphenol) as a vibration damping agent. A raw material and a vibration damping material composition were prepared under the same conditions. Table 5 shows the evaluation results.

Comparative Example 22
The performance of the organic polymer matrix alone was evaluated and is shown in Table 5.

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 (15)

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),
A represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom, the chain hydrocarbon group having an aromatic group, or an alicyclic carbon group having 5 to 8 carbon atoms. A hydrogen group,
B is a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom;
A and B may be the same or different from each other,
R ₁ , R ₂ and R ₃ are each a hydrocarbon group having 3 or less carbon atoms, an alkylol group or an aldehyde group, which may be the same or different, and p, q and r are each an integer of 0 to 3 And may be the same or different from each other,
X is a halogen atom, s, t and u are each 0 or 1, and may be the same or different from each other;
x, y and z are each an integer of 1 to 3 and may be the same or different from each other, and n is 0 to 200. )
A vibration damping material composition characterized by being a phenolic compound represented by the formula: An organic polymer matrix material is a vibration damping material composition comprising a vibration damping agent and an inorganic filler and / or an organic filler, wherein the vibration damping agent comprises:
The following general formula (I):

(In the general formula (I),
A represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom, the chain hydrocarbon group having an aromatic group, or an alicyclic carbon group having 5 to 8 carbon atoms. A hydrogen group,
B is a chain hydrocarbon group having 1 to 3 carbon atoms which may contain a sulfur atom and / or an oxygen atom;
A and B may be the same or different from each other,
R ₁ , R ₂ and R ₃ are each a hydrocarbon group having 3 or less carbon atoms, an alkylol group or an aldehyde group, which may be the same or different, and p, q and r are each an integer of 0 to 3 And may be the same or different from each other,
X is a halogen atom, s, t and u are each 0 or 1, and may be the same or different from each other;
x, y and z are each an integer of 1 to 3 and may be the same or different from each other, and n is 0 to 200. )
A vibration damping material composition characterized by being a phenolic compound represented by the formula: The organic polymer matrix material is a vinyl acetate resin, ethylene-vinyl acetate resin, epoxy resin, alkyd resin, polyester resin, polyurethane resin, polycarbonate resin, polylactic acid resin, polyether resin, ethylene -Methacrylate-based resin, acrylate-methacrylate-based resin, acrylonitrile-styrene-based copolymer, acrylonitrile-butadiene-styrene-based resin, acrylic rubber, butyl rubber, halogenated polyolefin, polyethylene, at least selected from the group consisting of polypropylene The vibration damping material composition according to claim 1 or 2, which is a kind of a high molecular compound. The vibration damping material composition according to claim 1 or 2, wherein the organic polymer matrix material is an acrylic rubber or an acrylate-methacrylate resin. 3. The vibration damping material composition according to claim 1, wherein the organic polymer matrix material is a polylactic acid resin or a mixture of a polylactic acid resin and an acrylic rubber. The said vibration damping agent is a phenolic compound with little steric hindrance, and is a compound having a chemical structure that does not have a branched hydrocarbon group having 4 or more carbon atoms at any position adjacent to both hydroxyl groups. 3. The vibration damping material composition according to 1 or 2. 3. The vibration damper according to claim 1, wherein A and B in the general formula (I) representing the vibration damping agent are each a chain hydrocarbon group bonded at the 2- or 4-position to the hydroxyl group. 4. Material composition. The bonding position of R ₁ , R ₂ and R _{3 in} the general formula (I) is at least one of the 2-position, 4-position or 5-position with respect to the hydroxyl group, and is the same or different from each other ( However, the case where A or B is bonded to the position is excluded.) The vibration damping material composition according to claim 1 or 2. The phenolic compound,
2,2'-methylenebis (4-methylphenol);
2,2'-methylenebis (4-ethylphenol);
2,2′-methylenebis (4-propylphenol);
2,2'-methylenebis (4-chlorophenol);
4,4′-methylenebis (2,5-dimethylphenol);
4,4'-methylenebis (2-methyl-5-ethylphenol);
4,4′-methylenebis (4-methyl-5-propylphenol);
2,6-bis (2-hydroxy-5-methylphenyl) -4-methylphenol;
2,2′-bis (4-hydroxy-3-methylphenyl) propane;
1,1′bis (4-hydroxyphenyl) cyclohexane;
α, α ′ (4-hydroxyphenyl) -1,4-diisopropylbenzene;
The vibration damping material composition according to any one of claims 6 to 8, wherein the composition is at least one phenolic compound selected from the group consisting of: The vibration damping material composition according to any one of claims 1 to 9, wherein the amount of the vibration damping agent is 5 to 70% by weight based on the total weight of the vibration damping material composition. The vibration-damping material composition according to any one of claims 2 to 8, wherein the inorganic filler is at least one inorganic compound selected from the group consisting of a basic inorganic filler and an acidic inorganic filler. The damping material composition according to claim 2, wherein the amount of the inorganic filler is 2 to 70% by weight based on the total weight of the 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 damping material composition according to claim 1, wherein the damping material composition is a coating film applied to a structure.

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