JP2000281838A - High damping material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high damping material composition excellent in workability while retaining high damping property. SOLUTION: This high damping material composition comprises 100 pts.wt. base polymer having at least one of acidic and basic polar side chains, 5-100 pts.wt. damping property-imparting agent and 10-200 pts.wt. tackifier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-attenuation material composition, and more particularly, to a sound insulation wall of an acoustic room,
The present invention relates to a high-attenuation material composition useful as a vibration-damping material or a sound-insulating material that absorbs vibration and noise applied to a sound-insulating partition of a building structure, a sound-insulating wall of a vehicle, and the like.

[0002]

2. Description of the Related Art Generally, a high damping material composition is used.
Polymer materials exhibit typical viscoelastic behavior
When the material minute part vibrates for some reason,
Complex sine strain (ε^*) Occurs
And this gives the complex sinusoidal stress (σ ^*) Occurs. Complex
Modulus of elasticity (E^*) Changes these ratios as shown in the following equation:
It was taken. Complex modulus of elasticity (E^*) = Complex sine stress (σ^*) / Complex positive
Chord distortion (ε^*)

The real part of the complex elastic modulus (E ^* ) is the storage elastic modulus (E ') related to the elastic properties of the polymer material.
The imaginary part of the complex elastic coefficient (E ^* ) is defined as a loss elastic coefficient (E ″) related to the viscous property of the polymer material.
Is defined as The loss tangent (tan δ) is obtained by taking these ratios as shown in the following equation. Loss tangent (tan δ) = loss elastic modulus (E ″) / storage elastic modulus (E ′)

[0004] The loss tangent (tan δ) is one of the factors that determine the soundproofing and vibration-damping characteristics. The higher the value, the more the mechanical energy is absorbed or released as electric or thermal energy, resulting in excellent sound absorption. It is known to exhibit mechanical properties such as vibration control and vibration damping. Conventionally, a value obtained as a loss tangent (tan δ) of a high attenuation material composition is 0.5 or more. As the high attenuation material composition satisfying the above tan δ ≧ 0.5, for example, a polymer composite material is known.
The above-mentioned polymer-based composite material has a polymer alloy or a polymer compound having a polymer network structure as a base polymer. A filler (mica or the like) or a plasticizer is added to the base polymer, and the polymer is obtained through a predetermined manufacturing process. It was done. Specific polymer compounds used as the base polymer include, for example, various rubber materials, polymer resin materials (polystyrene, polyisobutylene, polymethyl methacrylate, polyvinyl chloride, polyester, polytetrafluoroethylene, etc.) And an elastomer resin material.

[0005]

Although the above high damping material compositions meet the conventional required characteristics (tan δ ≧ 0.5), they do not meet the requirements for the environment in which they are used or their applications. Tanδ (tanδ ≧ 2.
0, more preferably tan δ ≧ 2.5) is desired. Therefore, a large amount of a tackifier or a softener is added to the base polymer to prepare a high attenuation material composition having a tan δ of more than 2.0.

However, when a large amount of a tackifier or a softener is blended in this way, the kneaded material becomes highly tacky,
It easily adheres to a kneading device such as an intermixer, and has extremely poor workability. In addition, since the tackifier and the softener have a low molecular weight and do not have entanglement, the tan δ peak is sharpened, the kneaded material is softened near the glass transition temperature (Tg), and the fluidity is increased. Loss coefficient η>
There is also a disadvantage that the temperature range of 0.1 is extremely narrow. As described above, a high damping material composition excellent in processability while maintaining high damping property has not yet been obtained.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a high-damping material composition excellent in processability while maintaining high damping.

[0008]

In order to achieve the above object, the high attenuation material composition of the present invention comprises the following (A)
It is a high attenuation material composition containing the component (C), wherein the content of the component (B) is set in a range of 5 to 100 parts by weight based on 100 parts by weight of the component (A). The content of the component (C) is set in the range of 10 to 200 parts by weight based on 100 parts by weight of the component (A). (A) A base polymer having at least one polar side chain of acidic or basic. (B) a damping agent. (C) a tackifier.

That is, the present inventors have conducted intensive studies to obtain a high-damping material composition excellent in processability while maintaining high damping. First, as a result of exploring a base polymer having excellent compatibility with the damping agent (component B), the specific base polymer (component A) has excellent compatibility with the damping agent (component B). I found out. Then, it was found that when the tackifier (C component) is used together with the specific base polymer (A component) and the damping agent (B component), high damping property can be exhibited. However, the above tackifier (component C)
When a large amount of is mixed, as described above, the tackiness of the kneaded material becomes high and the processability is inferior. Therefore, while studying a suitable blending ratio of the tackifier (C component),
Research was also conducted on a suitable compounding ratio of the above-mentioned damping agent (component B). As a result, it contains the specific base polymer (component A), the damping agent (component B), and the tackifier (component C), and further includes the damping agent (component B) and the tackifier. The high-damping material composition in which the content ratio of the (C component) is set to a specific range can exhibit high damping property, and the kneaded material has low tackiness, excellent workability, and broad tan δ peak. That is, they found that the temperature range of the loss coefficient η> 0.1 was 40 ° C. or more and was suitable for use in a wide temperature range, and reached the present invention.

[0010] By selecting specific base polymer (component A) and attenuating agent (component B), more excellent damping properties can be obtained.

[0011] In addition to the components A to C, a filler (D
When the component (1) is blended, the specific gravity of the kneaded material becomes large, and for example, when used as a viscoelastic layer of an unrestricted vibration damping material, excellent sound insulation can be obtained without impairing the vibration damping property.

[0012]

Next, embodiments of the present invention will be described in detail.

The high damping material composition of the present invention comprises a specific base polymer (A component), a damping agent (B component),
It can be obtained using a tackifier (component C).

As the specific base polymer (component A), for example, acrylic rubber, ethylene-acryl rubber, ethylene-vinyl acetate rubber, chlorinated polyethylene,
Examples thereof include polyvinyl chloride, acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber, chlorinated butyl rubber, styrene-butadiene copolymer rubber (SBR), styrene-isoprene-styrene copolymer, and the like. Used together. Among these, NB is preferred in terms of compatibility with the damping agent (component B).
R, chlorinated butyl rubber, and SBR are preferably used.

The damping agent (component B) used together with the specific base polymer (component A) is not particularly limited. For example, hindered phenol compounds,
Phosphorous ester compounds, benzothiazole compounds, amine compounds and the like are preferably used. These may be used alone or in combination of two or more.

The hindered phenol compounds include tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, which is an antioxidant.
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), pentaerythrityl-tetra [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5
-Methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2-[(3-
Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6 -Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -benzene, 1,6-
Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,
2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate],
2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-
6-t-butylphenol), 4,4'-thiobis (3
-Methyl-6-t-butylphenol), butylated reaction product of p-cresol and dicyclopentadiene, 2,
5-di-t-butylhydroquinone, 2,5-di-t-
1,4 which is an ultraviolet absorber such as amyl hydroquinone
-Bis (4-benzoyl-3-hydroxyphenoxy)
1- [2- {3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxy {ethyl] -4- {3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyloxy {-2,2,6,6-tetramethylpiperidine and the like. These may be used alone or in combination of two or more. Among them, 2,2'-methylenebis (4-methyl-6-t-butylphenol) [Nocrack NS-6, manufactured by Ouchi Shinko Chemical Co., Ltd.] is preferably used.

As the phosphite compound,
For example, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butanetriphosphite and the like. These may be used alone or in combination of two or more.

As the benzothiazole compound,
For example, N-cyclohexyl-2-benzothiazolylsulfenamide and the like can be mentioned.

Examples of the amine compound include a substituted diphenylamine represented by the following general formula (1).

[0020]

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The content ratio of the attenuating agent (component B) must be set in the range of 5 to 100 parts with respect to 100 parts by weight (hereinafter abbreviated as "part") of the base polymer (component A). Preferably it is 30 to 50 parts. That is, if it is less than 5 parts, the damping property is poor, and if it exceeds 100 parts, the blooming property is poor.

The tackifier (component C) used together with the above components A and B is not particularly limited. Examples thereof include petroleum hydrocarbon resins, rosins, coumarone resins, phenol resins, ketone resins, and dicyclopentadiene resins. , Maleic acid resin, esterified rosin, epoxy resin, urea resin, melamine resin and the like are preferably used. These may be used alone or in combination of two or more.

The mixing ratio of the tackifier (component C) is as follows:
10 to 20 based on 100 parts of base polymer (A component)
It is necessary to set in the range of 0 parts, preferably 50 to 1
50 parts. That is, if it is less than 10 parts, the damping property is poor, and if it exceeds 200 parts, workability deteriorates.

The high damping material composition of the present invention includes the above-mentioned A to
It is preferable to blend a filler (D component) together with the C component. The filler (D component) is not particularly limited, and includes, for example, mica, calcium carbonate, graphite,
Carbon fiber, glass fiber, pulverized paper, polyethylene terephthalate (PET) fiber, polyamide (PA) fiber, clay, talc, husk, barium sulfate, iron powder, ferrite, and the like are preferably used. These may be used alone or in combination of two or more. Among these, barium sulfate, iron powder, and ferrite are preferably used because the specific gravity of the compound is increased and sound insulation can be imparted without impairing vibration damping.

The mixing ratio of the inorganic filler (D component) is as follows:
It is preferably set to 700 parts or less with respect to 100 parts of the base polymer (A component), particularly preferably 50 to 5 parts.
The range is 00 parts. That is, if it exceeds 700 parts,
This is because workability deteriorates.

The high attenuation material composition of the present invention may contain a crosslinking agent, a crosslinking accelerator, and a crosslinking aid in addition to the above-mentioned components. Thus, dynamically cross-linking the base polymer (component A) using a cross-linking agent or the like is extremely effective when the adhesiveness of the kneaded material cannot be sufficiently suppressed.

Examples of the crosslinking agent include a sulfur-based crosslinking agent, a triazine-based crosslinking agent, a metal soap-based crosslinking agent, an amine-based crosslinking agent, a carbamate salt-based crosslinking agent, and an imidazole-based crosslinking agent. As the crosslinking accelerator, for example,
Crosslinking accelerators such as thiurams and thiazoles are preferably used. Examples of the crosslinking aid include ZnO (two types of zinc oxide) and the like.

Further, the high attenuation material composition of the present invention includes an antioxidant, an antioxidant, a plasticizer, a processing aid, a coloring agent (pigment, dye), a brightener, a flame retardant, a foaming agent, a foaming aid. Agents, anti-ozonants, anti-blocking agents, weathering agents, heat-resistant agents,
A dispersant, a compatibilizer, a surfactant, an antistatic agent, a lubricant and the like can be appropriately blended.

Examples of the plasticizer include dioctyl phthalate (DOP), paraffin oil and the like. Examples of the processing aid include stearic acid and the like.

The high attenuation material composition of the present invention can be obtained, for example, by kneading the above components using a kneading device such as a kneader with a pressure lid (intermixer). When a crosslinking agent, a crosslinking accelerator, or the like is blended, the mixture can be obtained by heating under predetermined conditions to dynamically crosslink the base polymer (A component), and then kneading.

Next, examples will be described together with comparative examples.

First, prior to Examples and Comparative Examples, the following materials were prepared.

[Base polymer (component A)] Chlorinated butyl rubber (chlorobutyl 1 manufactured by Nippon Butyl Co., Ltd.)
066)

[Attenuating agent (component B)] (Amine compound) Substituted diphenylamine represented by the general formula (1) (Naugard 44, manufactured by Shiraishi Calcium Co., Ltd.)
5)

(Hindered phenol compound) 2,
2'-methylenebis (4-methyl-6-t-butylphenol) [Nocrack NS-6, manufactured by Ouchi Shinko Chemical Co., Ltd.]

[Filler (D component)] Mica (Kuraray Co., Ltd., Clarite Mica c30) Calcium carbonate (Bikita Powder Chemical Industry Co., Ltd., Whiten S)
B)

[Tackifier (C component)] Petroleum hydrocarbon resin (Arukawa Chemical Co., Ltd., Alcon P7)
0) ・ Petroleum hydrocarbon resin (Arukawa Chemical Co., Ltd., Alcon P9)
0) ・ Coumarone resin (Nippon Steel Chemical Co., Ltd., Esculon G90) ・ Phenolic resin (Hitachi Chemical Industry Co., Ltd., Hitachil 1
501) ・ Straight asphalt 80-100 (JIS K
2207) ・ Blown asphalt 10-20 (JIS K22)
07)

[Crosslinking Aid] ZnO (2 types of zinc oxide)

[Crosslinking accelerator]-Thiuram-based crosslinking accelerator (Sunuchira TT-G, manufactured by Ouchi Shinko Chemical Co., Ltd.)-2-mercaptobenzothiazole (Noxeller M, manufactured by Ouchi Shinko Chemical Co., Ltd.)

[0040]

Examples 1 to 17 and Comparative Examples 1 to 4 The components shown in the following Tables 1 to 4 were blended in the proportions shown in the same table, and were mixed at 60 ° C. using a kneader with a pressure lid (intermixer). At 10
Kneaded for minutes. In Examples 6, 8, and 10, a crosslinking agent and a crosslinking accelerator were mixed, heated to 150 ° C. to perform dynamic crosslinking for 5 minutes, and then kneaded for 10 minutes.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

Using the kneaded products of the example product and the comparative product thus obtained, comparative evaluation of each characteristic was performed according to the following criteria. These results are shown in Tables 5 to 8 below.

[Tan δ] frequency 10 Hz, distortion 10 μ
The measurement was performed under the condition of m using a dynamic viscoelasticity measuring device (DMA manufactured by TA Instruments).

[Flow Temperature] Using the above DMA, the flow temperature was read from the storage elastic modulus (E ').

[Workability] The ease of taking out each of the above kneaded materials from the kneader was evaluated. The evaluation result is
The following is displayed. ：: No stickiness, very easy to take out △: Slightly sticky, but easy to take out ×: Lots of stickiness, extremely difficult to take out

[Loss Coefficient] For each of the above kneaded materials, the storage elastic modulus (E ') at room temperature was 1.0 × 10 ⁹ dyn / cm.
^If it exceeds ² , it is an unconstrained damping material. If it has a storage elastic modulus (E ') of 1.0 × 10 ⁹ dyn / cm ² or less, it is a constrained damping material. Each loss coefficient (η) was measured using a measuring machine (Matsushita Intertechno).

(Unconstrained Damping Material) A viscoelastic layer (thickness: 2 mm) made of each of the above kneaded materials was formed on a substrate (SPCC) having a thickness of 0.8 mm. 200
mm × 10 mm).

(Constrained vibration damping material) A viscoelastic layer (1.5 mm thick) made of each of the above kneaded materials was formed on a 0.8 mm thick substrate (SPCC), and a 0.1 m thick layer was further formed thereon.
m aluminum foil, and restrained damping material (size: 2
(00 mm × 10 mm).

[Bloom property] White fire (precipitate) on the surface when the sheet was allowed to stand at room temperature for one week was visually evaluated. The evaluation results were displayed as follows. ：: No surface white fire ×: Surface white fire

[Sound insulation] Based on JIS A1419, transmission loss (sound insulation) was evaluated. That is, the measurement was performed by attaching a vibration damping sheet having a thickness of 2 mm to a gypsum board having an areal density of 20 kg / m ² . Examples 1 to 6, 11, 1
2, 15 to 17 and Comparative Examples 1 to 4 have a thickness of 0.2 mm.
Was measured with an aluminum foil constraining layer.

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

[Table 8]

From the results of Tables 5 to 8, the product of the example was
All have high tan δ peak values and excellent damping properties, excellent workability, blooming properties and sound insulation properties, and also have a loss coefficient η.
It can be seen that the temperature range of> 0.1 is 40 ° C. or more, which is suitable for use in a wide temperature range.

On the other hand, the product of Comparative Example 1 was a tackifier.
Poor workability due to too high proportion of (C component)
I understand. The product of Comparative Example 2 has a distribution of the tackifier (component C).
The tan δ peak value is low and attenuated because the mixing ratio is too small.
And the loss coefficient η _MAXIs 0.1 or less
I understand. Comparative Example 3 is a product of the damping agent (B component).
The tan δ peak value is low due to too small a proportion.
Poor decay and loss factor η_MAXIs less than or equal to 0.1
You can see that. Comparative Example 4 is an attenuation imparting agent (component B)
Is too poor, resulting in poor blooming properties.
Call

[0060]

As described above, the high damping material composition of the present invention contains a specific base polymer (component A), a damping agent (component B) and a tackifier (component C). The compounding ratio of the above-mentioned damping agent (component B) and tackifier (component C) is set in a specific range. Therefore, while being able to express high damping,
The kneaded material has low adhesiveness, excellent workability, and tan δ
The peak becomes broad, and the temperature range where the loss coefficient η> 0.1 is 40 ° C. or more, which is suitable for use in a wide temperature range.

By selecting specific base polymers (component A) and attenuating agents (component B), more specific damping properties can be obtained.

In addition to the components A to C, a filler (D
When the component (1) is blended, the specific gravity of the kneaded material becomes large, and for example, when used as a viscoelastic layer of an unrestricted vibration damping material, excellent sound insulation can be obtained without impairing the vibration damping property.

The high damping material composition of the present invention, which is excellent in such a manner, has a very wide range of application, and can be used to reduce vibration and noise applied to sound insulation walls of acoustic rooms, sound insulation partitions of building structures, sound insulation walls of vehicles, and the like. It is useful as a damping material and soundproofing material to absorb. Further, the high attenuation material composition of the present invention, for example,
Seismic isolation materials, soles, tennis rackets, table tennis rackets, baseball bats, golf clubs, hockey clubs, etc., gripping materials for grips, electric devices, CD reading parts, cushioning materials for personal computers, etc. It can also be used as a damping material for faucet hammering.

Continued on the front page (72) Inventor Kazunobu Hashimoto 3600, Gezu, Kitai-gaiyama, Komaki, Komaki, Aichi Prefecture F-term in Tokai Rubber Industries Co., Ltd. BK00X BP01W CC03X CC16X CC18X CD00X CE00X CF063 CJ00X CL063 DA017 DA027 DA087 DC007 DE237 DG047 DJ037 DJ047 DJ057 DL007 EE036 EE056 EJ016 EJ036 EJ046 EN066 EU086 EU196 EV076 EV286 EW066 FA043 FA047 FD013 FD017 FD020 FD030 FD046 FD056 FD070 FD076 FD080 FD090 FD10 FD130 FD140 FD150 FD17 FD310 FD320 GL00

Claims (4)

[Claims] 1. A high attenuation material composition comprising the following components (A) to (C), wherein the content of the component (B) is 5 to 100 with respect to 100 parts by weight of the component (A). A high-attenuation material, wherein the content of the component (C) is set in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the component (A). Composition. (A) A base polymer having at least one polar side chain of acidic or basic. (B) a damping agent. (C) a tackifier. 2. The base polymer as the component (A) is an acrylic rubber, an ethylene-acryl rubber, an ethylene-vinyl acetate rubber, a chlorinated polyethylene, a polyvinyl chloride, an acrylonitrile-butadiene copolymer rubber, a butyl rubber,
The high attenuation material composition according to claim 1, wherein the composition is at least one selected from the group consisting of styrene-butadiene copolymer rubber and styrene-isoprene-styrene copolymer. 3. The damping agent as the component (B) is at least one selected from the group consisting of hindered phenol compounds, phosphite compounds, benzothiazole compounds and amine compounds. The high damping material composition according to claim 1. 4. The high attenuation material composition according to claim 1, further comprising the following component (D) in addition to the components (A) to (C). (D) a filler.