JP2769361B2 - Composition having damping properties and damping material molded therefrom - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composition having a vibration damping property and a vibration damping material formed from the composition, and more specifically to a petroleum resin. A composition having vibration damping properties by mixing an amount of asphalt and mica, and molding the composition to form a building;
The present invention relates to a vibration damping property for absorbing vibration energy of a vehicle or the like and having excellent adherence followability to unevenness of a base material.

(Conventional technology and its problems) Conventionally, it has been known to use an asphalt-based composition as a vibration damping material for absorbing various vibrations and shocks, particularly for absorbing vibration energy of buildings, vehicles, and the like. ing.

Vibration suppression is to convert the mechanical energy into thermal energy and reduce it when the object is deformed.
The damping material reduces the amplitude at the time of resonance and reduces sound radiation and stress.

Reduces solid-borne sound and vibration energy propagation.

Attenuates free vibration and reduces impact noise. It is known to fulfill such functions.

The most widely used method of damping a structural element that generates vibration, for example, a building, a vehicle, or the like, is a method of applying a polymer viscoelastic material such as asphalt to the surface of a structural material. Japanese Patent Publication No. 52-50522 and Japanese Patent Publication No. 56-5469 are also examples, and all of these inventions increase the damping loss coefficient of asphalt used as a vibration damping material. In addition, it is characterized in that a specific compounding agent is compounded.

Further, Japanese Patent Application Laid-Open No. 57-29702 discloses a coating material for vibration isolation and waterproofing, in which asphalt is a main component, and mica having an aspect ratio of 90 or more is dispersed in a multilayer shape. Japanese Patent Application Laid-Open No. 58-28034 discloses binders, fibrous, powdery, and scales containing asphalt and / or a thermoplastic synthetic resin as a main component and a rubber component and / or a wax as a modifier component. Damping material obtained by spraying a particulate material of a component comprising at least one or more fillers selected from fillers in a form of a substrate and forming a sheet-like vibration-damping layer by thermal or physical operation However, JP-A-52-39723 further discloses asphalt 60 to 8
A vibration damping material comprising 0 parts by weight, 3 to 9 parts by weight of a petroleum resin, and 5 to 15 parts by weight of organic short fibers is disclosed.

However, all of these damping materials have a large asphalt content, and not only do not have sufficient damping performance, but it is difficult to adjust the peak temperature of the damping performance, and due to heating during kneading and construction, the unique characteristics of asphalt It is a major drawback that it is difficult to handle, for example, it emits odor.

(Object of the Invention) Accordingly, an object of the present invention is to provide a composition having a high damping performance and having a small asphalt smell during kneading.

Still another object of the present invention is to provide a vibration damping material having excellent adherence followability to a substrate obtained by molding the composition.

(Means for Solving the Problems) According to the present invention, 100 parts by weight of an aromatic petroleum resin obtained from an isopropenyltoluene petroleum resin or a fraction containing an aromatic unsaturated hydrocarbon having 9 carbon atoms. And asphalt 100 to 500 parts by weight, and the aspect ratio is 50 to
The present invention provides a composition having a damping property, characterized by containing at least 90 to 400 parts by weight of mica (where the amount of mica is smaller than the amount of asphalt).

According to the present invention, there is also provided a vibration damping material obtained by molding the above-mentioned vibration damping composition.

(Action) The present invention provides a composition having excellent vibration damping performance by blending the proportion of petroleum resin in the composition having vibration damping properties so as to be at least 10% by weight and at most 50% by weight.
This is based on the finding that by selecting mica as a filler and blending it in an amount smaller than the blending amount of asphalt, a vibration damping material having excellent close contact followability can be obtained.

(Description of Preferred Embodiment) Isopropenyltoluene-based petroleum resin, which is one of the petroleum resins used in the present invention, is used for isopropenyltoluene homopolymer and isopropenyltoluene during petroleum refining and petroleum cracking. Resins obtained by copolymerizing the resulting fractions, in particular the fractions containing unsaturated hydrocarbons having 4 and 5 carbon atoms (C4, C5 fractions) in the presence of Friedel-Crafts catalysts, or those which are modified or hydrogenated Resin. The C4 and C5 fractions are usually 100 parts by weight or less, preferably 5 parts by weight, based on 100 parts by weight of isopropenyl toluene.
It is used in amounts of up to 100 parts by weight.

The other aromatic petroleum resin has a boiling point of 140 to 280 ° C.
(C9 fraction) containing an aromatic unsaturated hydrocarbon having 9 carbon atoms (for example, styrene, indene, vinyltoluene, etc.) having a boiling point of-
A fraction containing 10 to 20 ° C. olefins and diolefins having 4 carbon atoms (C4 fraction) and a fraction containing 15 to 60 ° C. and containing 5 olefins and diolefins (C5 fraction) ). For example, a resin obtained by polymerizing or copolymerizing these fractions in the presence of a Friedel-Crafts catalyst, or a C9 fraction and a cyclic diolefin such as dicyclopentadiene in the presence of a Friedel-Crafts catalyst Resins obtained by copolymerization or thermal polymerization, or modified or hydrogenated resins thereof.

In the above-mentioned isopropenyltoluene petroleum resin and aromatic petroleum resin, modification can be performed using α, β-unsaturated carboxylic acid or its anhydride.

In view of obtaining a particularly excellent vibration damping effect, the isopropenyl toluene-based petroleum resin preferably has a softening point (ring and ball method) in the range of 30 to 140 ° C., and the aromatic petroleum resin has a softening point. Is preferably 80 to 150 ° C.

In the present invention, a particularly preferred isopropenyl toluene-based petroleum resin has the following physical properties.

(A) Softening point 30 to 140 ° C (preferably 70 to 125 ° C) (ring and ball method) (b) Bromine value 3 to 20 (c) Number average molecular weight 500 to 1200 (d) Hue Gardner color number (melting method) 1 to 5 In the present invention, particularly preferred aromatic petroleum resins have the following physical properties.

(A) Softening point 80 to 150 ° C (preferably 80 to 120 ° C) (ring and ball method) (b) Bromine value 10 to 60 (c) Number average molecular weight 300 to 2500 (preferably 400 to 1500) (d) Hue Gardner color number (melting method) 3 to 14 In the composition having a vibration damping property of the present invention, when the above petroleum resin is mixed, the peak value of the damping value at room temperature to 40 ° C. exceeds 11%. Since the damping value in this temperature range is high, it can be suitably used particularly as a vibration damping material for buildings, vehicles, and the like.

The petroleum resins described above are each manufactured by a method known before the present application, and as one example, isopropenyl toluene or isopropenyl toluene.
The petroleum resin obtained from the C ₄ and C ₅ fractions, are prepared by the following method.

As isopropenyltoluene, ortho-, meta-, or para-isomers and mixtures thereof are used. In particular, the para isomer is 20 to 60%, and the meta isomer is 40 to 80%.
%, And a mixture of 0 to 10% ortho isomer is preferably used. Also, the purity of isopropenyl toluene is 80% by weight.
In addition to the above, a small amount of styrene, vinyl toluene,
It may contain a polymerizable monomer such as α-methylstyrene.

Fractions containing unsaturated hydrocarbons having 4 and 5 carbon atoms (C ₄ and C ₅ fractions) by-produced during petroleum refining and petroleum cracking have a boiling point range of -15 to + 45 ° C under normal pressure. Minutes
1-butene, isobutylene, 2-butene, 1,3-butadiene, 1-pentene, isoprene, 2-methyl-1-butene, 3-methyl-1-butene, 2-pentene, isoprene, 1,3-pentadiene, Contains polymerizable monomers such as cyclopentadiene. It is possible to use not only a fraction containing a polymerizable monomer selected from C ₄ and C ₅ fractions, but also a C ₄ fraction excluding butadiene and a C ₅ fraction excluding isoprene and cyclopentadiene. Such a fraction can be mixed with 100 parts by weight of
To 100 parts by weight.

The catalyst used for the copolymerization is generally known as a Friedel-Crafts catalyst, and includes, for example, various complexes of aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride, and boron trifluoride. These catalysts are preferably used in an amount of usually 0.1 to 3.0% by weight, and particularly preferably 0.5 to 1.5% by weight, based on the raw material.

In the copolymerization, the unsaturated hydrocarbon contained in the C ₄ and C ₅ fractions becomes the solvent as it is.However, in order to remove the reaction heat and suppress the viscosity of the polymerization liquid, the solvent is used to initialize the polymerizable monomer. The concentration is preferably about 30 to 50% by weight. Suitable solvents include, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclopenta, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, ethylbenzene and mesitylene; or These mixtures can be mentioned.

The polymerization temperature varies depending on the raw material composition, but is usually selected from the range of -5 to + 70 ° C (preferably -50 to 50 ° C).

As the polymerization mode, either a batch type or a continuous type can be adopted. Further, multi-stage polymerization can be performed.

After completion of the polymerization, the catalyst is decomposed with an aqueous alkali solution or methanol, washed with water, and unreacted oil and solvent are removed by stripping.
The desired resin at 30 to 140 ° C. can be obtained.

Examples of the asphalt used in the present invention include straight asphalt, blown asphalt, a mixture of 50 to 80% by weight of blown asphalt and 50 to 20% by weight of straight asphalt, or an asphalt for waterproofing such as blown asphalt modified with oil and fat. Among them, oil- and fat-modified blown asphalt having a penetration of 20 to 30 is preferably used.

The fat-modified blown asphalt is obtained by adding animal or vegetable oils such as non-drying animal oil (for example, beef tallow), drying animal oil (for example, squid oil), semi-dry vegetable oil (for example, soybean oil), drying vegetable oil (for example, linseed oil) or the like to the blown asphalt. It can be obtained by adding and mixing fatty acid pitch (eg, rapeseed oil) or the like, or by compounding in the process of producing blown asphalt.
The content of animal and vegetable fats and oils or fatty acid pitch in the fat and oil modified asphalt is usually preferably 1 to 20% by weight.

Asphalt is 100 to 100 parts by weight of petroleum resin.
500 parts by weight, preferably 150 to 400 parts by weight are blended. By suppressing the amount of asphalt to petroleum resin at most 5 times, in other words, by increasing the ratio of petroleum resin in the whole composition, the vibration damping performance, that is, the damping value is increased, Since the asphalt in it functions favorably as a plasticizer, it is easy to adjust the dumping peak temperature.The mica used in the present invention is an inorganic filler that is also used in conventional vibration damping materials containing asphalt as a main component. However, mica shows a synergistically increased damping value when melt-mixed in petroleum resin, which is completely different from other inorganic fillers. And the viscosity distribution based on JIS Z 8801 is 8
0% or more becomes more remarkable when 50 mesh pass mica is used. The amount of mica is 100
The weight is 90 to 400 parts by weight, preferably 140 to 300 parts by weight with respect to parts by weight. Is preferably smaller than the amount of asphalt.

The present invention is basically composed of the above three components. However, in order to make the appearance of the damping material supplied in the form of a sheet more beautiful and smooth, the defoaming of silicon oil or the like is performed. A composition having excellent vibration damping performance can be obtained by adding 0.01 to 0.5 part by weight of the agent to 100 parts by weight of petroleum resin, but after melt-kneading the petroleum resin and asphalt in advance, other compositions such as mica By kneading the above components, the dispersibility is good, and a homogeneous composition can be obtained in a short time.

Melt mixing is performed at 80 to 200 ° C., preferably 100 to 160 ° C.
A Brabender with a heating device at a temperature of 0 ° C. and at atmospheric pressure for 10 minutes to 1 hour, preferably 20 minutes to 40 minutes,
It is performed by a kneading device such as a mixing stirrer, a kneader, an extruder or a roll.

The vibration damping composition obtained by the present invention has a feature that, because a large amount of petroleum resin is used, it exhibits excellent damping value (vibration damping performance) and is easy to handle. It becomes more remarkable when an isopropenyltoluene or aromatic petroleum resin is used as the resin.

The composition having a vibration damping property of the present invention, within a range that does not impair the vibration damping performance, an inorganic or organic filler, a flame retardant,
Pigments, stabilizers and the like can be blended. Examples of fillers that can be blended include powdery fillers such as talc, clay, calcium carbonate, carbon, and zinc oxide, fibrous fillers such as asbestos, glass fibers, and carbon fibers, shirasu balloons, silica balloons, phenolic resin balloons, and the like. Flame retardants such as microballoons or synthetic resin powder, synthetic fiber waste, valve powder, crushed paper, etc. include antimony oxide, halogenated aromatic compounds, halogenated aliphatic compounds, magnesium hydroxide, aluminum hydroxide, boron oxide, phosphorus oxide Acid esters, red phosphorus, red phosphorus stabilized with aluminum hydroxide, ferrocene, ferrocene derivatives, iron acetylacetate, etc., and various known inorganic or organic pigments as pigments; , Phenolic, amine-based as well as known antioxidants and vibration damping materials Illustrated known weathering stabilizers such as amine required for use, it can be formulated as alone or in combination of two or more.

The composition having vibration damping properties of the present invention is formed into a sheet-shaped or block-shaped or other shaped article, and various machines and devices that generate vibration and noise by rotating and reciprocating motion, and housings thereof, bridges, and the like. It is used for applications such as pipes for structures, water supply, gas, etc., air conditioning ducts, and vibration damping materials for various vehicles. For example, it is the most suitable as a vibration damping material for vehicle panels such as buildings and automobiles. Is shown.

The vibration damping material of the present invention is usually kneaded with a kneading machine such as a two-roller equipped with a heating device known per se,
Rolled on a sheet having a thickness of 0.1 to 10 mm by a calender roll is supplied in a state of being cut into sheet pieces of about 1000 mm × 500 mm. Therefore, at this time, it is preferable to mix an antifoaming agent such as silicone oil as described above for the purpose of smoothing the sheet surface and improving the appearance. As a bonding method, there are used heat compression bonding by a roll, heat compression bonding by a heating blower, heat fusion adhesion in a non-pressure state, adhesion by an adhesive, and the like. Excellent restraint performance can be achieved even with a restrained type. Further, since the vibration damping material of the present invention has excellent vibration damping performance, it can exhibit a sufficient vibration damping effect in an extremely thin sheet shape of at most 1 to 1.5 mm. It is particularly suitable for use as a vibration damping material for panels and the like.
A sufficient vibration damping effect can be obtained with the use amount of 1 to 5 times.

As described above, the damping material of the present invention has a high damping value in a wide range of 0 ° C. to 60 ° C., and a frequency of 50 Hz to 50 ° C.
It has excellent vibration damping performance in the range of 1KHz.

The mica in the composition having a vibration damping property of the present invention increases the damping value in proportion to the blending amount, but as described above, makes the adhesion following property, which is an important element as a vibration damping material, better. Therefore, it is preferable that the blending amount is always smaller than the blending amount of asphalt.

(Effect of the Invention) According to the present invention, a damping composition having an increased damping value can be obtained in a wide temperature range of about 0 ° C to 60 ° C, and a damping material obtained from this composition can be obtained. Is excellent in the adherence followability adapting to the uneven surface of the base material. This vibration damping material can provide an effect of contributing to weight reduction of a building, a vehicle, and the like because a high level of vibration damping can be obtained by using a small amount in proportion to the conventional vibration damping material. .

(Examples) Hereinafter, the present invention will be described in detail based on examples.

In the examples, the damping value and the adhesion followability were measured by the following methods.

Damping value: The vibration damping ratio (damping value) of the first moment of bending (about 300 Hz) was determined by changing the measurement temperature by the two-point suspension resonance method.

The maximum value (C / C _c ) _{max of} the vibration damping ratio (damping value) for obtaining the vibration damping performance of the vibration damping material of the present invention and the temperature (T
_max ) are shown in Table 1.

Adhesion followability: corrugated steel substrate shown in Fig. 1 (span A between tops: 30 mm, inclination angle of waveform θ: 35 °, height of waveform B: 10 m)
m, a damping sheet cut into a size of 200 mm × 40 mm was placed on the top and bottom of the waveform (R: 8), and the adherence following property after heating in an oven at 150 ° C. for 30 minutes was observed. The state shown in FIG. 2, that is, a completely adhered state (the interval (X) between the corrugated bottom and the sheet bottom is 0): (◎), a state in which a slight gap is formed in the bottom (X is larger than 0 and 1 mm Below): (○), although considerable voids were formed at the bottom (X is larger than 1 mm and 3 mm or less): (△), hardly softened (X
Is larger than 3 mm): expressed as (X).

Reference Example (Production of isopropenyltoluene petroleum resin) 100 g of isopropenyltoluene (purity 99.2%) obtained by distillative separation from the acid fission product of cymene hydroperoxide in the cresol production process of cymene method, obtained from pyrolysis of petroleum naphtha C _4, C _5, which contains an unsaturated hydrocarbon which is
Charge an autoclave with 10 g of a fraction and 150 g of toluene,
BF ₃ phenol complex while maintaining the temperature at 0 ° C with stirring
1.5 g was added dropwise in about 10 minutes. Thereafter, stirring was continued for another 3 hours. Next, 50 ml of a 5% aqueous sodium hydroxide solution was added, and the mixture was vigorously stirred for 30 minutes to decompose the catalyst. The aqueous layer was separated, and the polymerized oil was washed with water until it became neutral. This gave 105 g of a pale yellow blocky resin as a residue. The composition of the starting monomers and the properties of the resulting resin were as follows.

Isopropenyltoluene composition o- isopropenyltoluene 5.3% m-isopropenyl toluene 60.4% p-isopropenyl 33.5% cymene 0.8% toluene C _4, C ₅ fraction composition C ₃ 1.5% isobutane 0.4% n-butane 1.3% 1- Butene 10.5% isobutylene 19.8% trans-2-butene 8.7% cis-2-butene 4.4% 1,3-butadiene 20.9% n-pentane 5.1% isoprene 5.6% 1,3-pentadiene 2.8% cyclopentadiene 3.1% other (boiling point 80 15.9% resin properties Hue 3 (Gardner, ASTM D 154-58), softening point 92 ° C
(Ring and ball method), number average molecular weight 730, bromine value 6 (ASTM D 1158
-57).

In Examples, the isopropenyltoluene-based petroleum resin obtained by the above method is referred to as "petroleum resin A".

Aromatic petroleum resin The following was used as the aromatic petroleum resin.

Obtained by polymerizing a fraction containing as a main component an aromatic unsaturated hydrocarbon having 9 carbon atoms obtained during naphtha cracking,
Softening point (ring and ball method) 120 ° C, Gardner color number (melting method) 1
0, an aromatic hydrocarbon resin having physical properties of a number average molecular weight of 1,000, a bromine number of 40, and a specific gravity of 1.07 (trade name: Mitsui Petrozin # 120, manufactured by Mitsui Petrochemical Industry Co., Ltd .; That.

A softening point (ring and ball method) of 100 ° C., a Gardner color number (melting method) of 13, obtained by polymerizing a fraction containing an aromatic unsaturated hydrocarbon having 9 carbon atoms as a main component obtained during naphtha cracking; Aromatic hydrocarbon resin having physical properties of a number average molecular weight of 500, a bromine number of 40 and a specific gravity of 1.07 (manufactured by Mitsui Petrochemical Industries, Ltd., trade name: Mitsui Petrosin # 100, which is referred to as "petroleum resin C" in Examples) .

A softening point (ring and ball method) of 80 ° C., a Gardner color number (melting method) of 13, obtained by polymerizing a fraction containing an aromatic unsaturated hydrocarbon having 9 carbon atoms as a main component obtained during naphtha cracking; Aromatic hydrocarbon resin having physical properties of number average molecular weight 450, bromine number 40 and specific gravity 1.07 (Mitsui Petrochemical Co., Ltd., trade name Mitsui Petrosin # 80, which is
"Petroleum resin D").

Aliphatic petroleum resin Aliphatic olefins obtained in the naphtha pyrolysis process, aliphatic olefins obtained by polymerizing a fraction containing an unsaturated unsaturated hydrocarbon composed mainly of diolefins as a main component, softening point 100 ° C, Gardner Color number (melting method) 9, number average molecular weight 1100, bromine value
35. Aliphatic hydrocarbon resin having physical properties of specific gravity 0.97 (trade name: Hiretz G-10, manufactured by Mitsui Petrochemical Industries, Ltd.)
0X, which is referred to as "petroleum resin E" in the examples).

Asphalt Oil-modified blown asphalt (penetration 20/30)… asphalt A straight asphalt (penetration 80/100)… asphalt B blown asphalt (penetration 20/30)… asphalt C Mica Aspect ratio 50 to 200 The particle size based on JIS Z 8801 is 80% or more and has a 50 mesh pass. Examples 1 to 9 and Comparative Examples 1 to 3 The blends shown in Table 1 were manufactured by Ashizawa Co., Ltd. A predetermined amount of petroleum resin and asphalt are charged into the roll and kneaded. When the kneading components begin to melt, mica is gradually added. When adding silicone oil, add it at the same time as mica. After about 15 minutes, when the materials have been sufficiently melt-kneaded and homogenized, the roll kneading is completed.

Next, the kneaded material was supplied to a calender roll while cooling, and a 2 mm-thick vibration damping sheet was prepared. The obtained vibration damping sheet was cut into a size of 32 mm × 300 mm and subjected to a physical property test.

 Table 1 shows the results.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a steel substrate for measuring the adherence following property of the damping material according to the present invention, and FIG. 2 is a cross-sectional view showing evaluation of the adherence following property of the damping material. 1 ... sheet-like vibration damping material 2 ... steel substrate

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenji Yokoyama 1-4-28 Mita, Minato-ku, Tokyo Nippon Electric Environmental Engineering Co., Ltd. (72) Yoshio Iida 1-4-28 Mita, Minato-ku, Tokyo No. Nippon Electric Environmental Engineering Co., Ltd. (56) References JP-A-51-105326 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 95/00 C08L 57/02 C08K 3/34

Claims (2)

(57) [Claims] (1) 100 parts by weight of an aromatic petroleum resin obtained from an isopropenyl toluene-based petroleum resin or a fraction containing an aromatic unsaturated hydrocarbon having 9 carbon atoms; 100 to 500 parts by weight of asphalt; A composition having vibration damping properties, comprising 90 to 400 parts by weight of mica having a ratio of 50 to 200 (however, the amount of mica is smaller than the amount of asphalt). 2. A vibration damping material formed from the composition according to claim 1.