JPH03212463A - Composition having vibration-damping property and vibration damper molded from the same composition - Google Patents

Abstract

PURPOSE:To obtain the title composition contributing to lightening in building material, automobile, etc., having further increased damping value, excellent freeze resistance, flex properties and adhesion-following properties by blending terpene-based resin with asphalt and filler in a specific ratio. CONSTITUTION:(A) 100 pts.wt. terpene-based resin (e.g. resin having 80-140 deg.C softening point prepared by polymerizing terpene monomer in the presence of catalyst) is blended with (B) 100-500 pts.wt., preferably 150-400 pts.wt. asphalt (preferably fat- and oil-modified blown asphalt) having 20-30 penetration and (C) 90-400 pts.wt., preferably 140-300 pts.wt. (with the proviso that an amount of the filler blended is smaller than that of the asphalt) to give the objective composition. The composition is molded to give a vibration damper.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a composition having vibration damping properties and a vibration damping material molded from the composition. A composition having vibration damping properties that is a mixture of asphalt and a filler, and a damping material for absorbing vibration energy of buildings, vehicles, etc. by molding the composition. Regarding.

(Prior art and its problems) It has been known that asphalt-based compositions have been used as vibration damping materials to buffer various vibrations and shocks, especially to absorb vibration energy from buildings, vehicles, etc. ing.

Vibration is the process of converting the mechanical energy of an object into thermal energy and reducing it when it deforms, and damping materials: ■ Reduce the amplitude during resonance and reduce sound radiation and stress.

■ Reducing solid-borne sound and vibration energy propagation.

■ It is known to perform functions such as damping free vibration and reducing impact noise.

The most widely used vibration damping method is to dampen structural elements that generate vibrations, such as buildings and vehicles.
This is a method of applying a polymeric viscoelastic material such as asphalt to the surface of the structural material. The techniques disclosed in Japanese Patent Publication No. 52-50522 and Japanese Patent Publication No. 56-5469 are also examples, and these inventions are designed to increase the damping loss coefficient of asphalt used as a vibration damping material. It is characterized by the fact that it contains specific ingredients.

Furthermore, Japanese Patent Application Laid-open No. 57-29702 discloses a coating material for vibration-proofing and waterproofing, which has asphalt as its main component and mica with an aspect ratio of 90 or more is dispersed therein in a multilayered manner. Published in Japanese Unexamined Patent Publication No. 58-28
Publication No. 034 states that a binder containing asphalt and/or a thermoplastic synthetic resin as a main component and a rubber component and/or a wax as a modified material component, and a fibrous, scale-like, and scale-like filler selected from among A vibration damping material is further disclosed in Japanese Patent Application Laid-Open No. 52-117, which is made by dispersing powder particles of at least one type of filler on a substrate and forming a sheet-like damping layer by thermal or physical manipulation. Publication No. 39723 discloses that a splitting material consisting of 60 to 80 parts by weight of asphalt, 3 to 9 parts by weight of petroleum resin, and 5 to 15 parts by weight of short organic fibers,
Each is disclosed.

However, all of these damping materials contain a large amount of asphalt, and not only do they not have sufficient damping performance, but they also have the unique characteristics of asphalt, such as difficulty in adjusting the peak temperature of vibration performance, and due to crosstalk and heating during construction. Its major drawback is its handling, including the fact that it emits odors.

Based on such conventional technology, the present inventors sought to create a damping composition that has high vibration damping performance and has less asphalt odor during cross-contact. It was discovered that a composition containing the above was able to achieve the above object, and a patent application was previously filed (Japanese Patent Application No. 83717 (Hei 1)).

Furthermore, in the process of retesting the invention and pursuing a composition with even better distribution control ability, the present inventors developed a composition in which a specific proportion of asphalt and filler were mixed with a terpene resin. The present invention was achieved based on the knowledge that the method has extremely excellent allocation performance.

(Object of the Invention) Therefore, an object of the present invention is to provide a composition that has extremely high vibration damping performance and has low asphalt odor during kneading.

Furthermore, another object of the present invention is to provide a vibration damping material having excellent adhesion followability to a base material obtained by molding the composition.

Means for Solving Problem C) The present invention has been made to achieve the above object, and
It is characterized by containing terpene resin, asphalt, and filler in specific proportions.

That is, according to the present invention, for 100 parts by weight of terpene resin, 100 to 500 parts by weight of asphalt and 9 to 400 parts by weight of filler (however, the amount of filler blended is smaller than the amount of asphalt blended) ), and a damping material obtained by molding the composition.

(Function) The present invention provides a composition with excellent vibration damping performance by blending the proportion of terpene resin in the composition having vibration damping properties to a minimum of 10% by weight and a maximum of 50% by weight. This was done based on the knowledge that by blending the filler in a smaller amount than the amount of asphalt, an allocation material with excellent adhesion followability can be obtained.

(Description of preferred embodiments) The terpene resin that can be used in the present invention is obtained by polymerizing natural or synthetic terpene monomers in the presence of a Friedelkraff catalyst, and has a softening point of 80 to 140°C.
of a terpene resin or other hydrocarbon resins, such as C4, C, fractions, within 50% by weight, preferably within 20% by weight (based on the total resin components) of the terpene resin, are added to the terpene resin, such as C4, C, fractions, etc., to the terpene resin. Any fraction with a boiling point range of -10 to 280°C, which is a by-product during the decomposition or reformation of petroleum, and a resin with a softening point of 80 to 120°C obtained by polymerization in the presence of Resins with a softening point of 40 to 160°C obtained by cationic polymerization or thermal radical polymerization in the presence of a catalyst, or resins modified from these resins, such as any boiling point range of 140 to 280°C. An aromatic product obtained by polymerizing a fraction containing as a main component an aromatic unsaturated hydrocarbon having 9 carbon atoms (for example, styrene, indene, vinyltoluene, etc.) (C9 fraction) in the presence of, for example, a Friedel Krach catalyst. hydrocarbon resins (aromatic petroleum resins), fractions containing mainly olefins and diolefins having 4 carbon atoms (C4 fraction) with a boiling point range of 10 to 20'C, or boiling point ranges of 15 to 60'C 'C
Aliphatic petroleum resins obtained by polymerizing a fraction containing mainly olefins and diolefins having 5 carbon atoms (C5 fraction) in the presence of a free-solat fluorine catalyst, C9 fraction and C4
A resin obtained by mixing fractions and/or C5 fractions and copolymerizing them in the presence of a free sol Talafluorocatalyst, and a resin obtained by copolymerizing the C9 fraction and a cyclic diolefin such as dicyclopentadiene in the presence of a Friedelkraff catalyst. A resin obtained by copolymerizing or thermally polymerizing a vinyl aromatic hydrocarbon such as styrene or a-methylstyrene and a C, CS fraction in the presence of a Friedelkraff catalyst. Aromatic petroleum resins or aliphatic resins, such as resins obtained by copolymerization, and resins obtained by modifying the above resins with α, β-unsaturated carboxylic acids or their anhydrides, or hydrogenating them. Petroleum resins can be mixed, especially those with a softening point (cyclic method) of 80 to 1
By using terpene hydrocarbon resin at 20℃,
Particularly excellent allocation effects can be obtained.

In the present invention, particularly preferred terpene-based hydrocarbon resins have the following physical properties.

fal Softening point 30 to 140°C (preferably 80 to 120°C) (ring and ball method) (b1 Hue Gardner color number (melting method) 1 to 5 In addition, in the present invention, a particularly preferred aromatic system to be mixed with the terpene resin Petroleum resin has the following physical properties.

fat Softening point 8o to 150'C (preferably 80 to 100'C) (ring and ball method) fbl bromine number
1o to 6°fC1 number average molecular weight 300 to 2500 (preferably 400 to 1500) (b) Hue Gardner color number (melting method) 3 to 14 In the composition having vibration damping properties of the present invention, the above terpene resin is The mixture has a peak damping value of more than 1% at room temperature to 40°C, and because the damping value is high in this temperature range, it is particularly suitable as a vibration damping material for buildings, vehicles, etc. It can be used for.

The terpene resin mentioned above can be produced by a method known before this application.

The asphalt used in the present invention is straight asphalt, blown asphalt, blown asphalt 5 to 80% by weight, and straight asphalt 5 to 80% by weight.
Asphalt for waterproofing work such as a mixture of 0 to 20% by weight or oil-modified blown asphalt can be exemplified, but among them, oil-modified blown asphalt with a penetration degree of 20 to 3 is preferably used.

This oil-modified blown asphalt is produced by adding non-drying animal oil (such as beef tallow) and drying animal oil (such as tallow) to blown asphalt.
(e.g., squid oil), semi-drying vegetable oil (e.g., soybean oil), drying vegetable oil (e.g., linseed oil), or their fatty acid pitch (e.g., rapeseed oil).
Alternatively, it can be obtained by compounding during the production process of blown asphalt. The content of animal and vegetable oil or fatty acid pitch in the fat-modified asphalt is usually preferably 1 to 20% by weight.

The amount of asphalt is 100 to 500 parts by weight, preferably 150 to 400 parts by weight, based on 100 parts by weight of terpene resin.
Parts by weight are blended. In this way, by suppressing the amount of asphalt to terpene resin to at most five times, in other words, by increasing the ratio of terpene resin in the entire composition, the vibration damping performance, that is, the damping value, increases. Since the asphalt in the composition functions suitably as a plasticizer, the damping peak temperature can be easily adjusted.

The fillers used in the present invention include powder fillers such as talc, clay, mica, graphite, calcium carbonate, carbon, and zinc oxide, fibrous fillers such as asbestos, glass fiber, and carbon fiber, shirasu balloon, and silica. Balloons, micro balloons such as phenolic resin balloons, synthetic resin powder, synthetic fiber waste, etc.
Among them, mica and graphite are preferably used in terms of allocation performance, and above all, mica and graphite (with an aspect ratio of 50 to 200 and a particle size distribution of 8801 based on JIS Z 8801)
The allocation performance is even better when using mica with 0% or more L of 50 mesh baths.

The blending amount of the filler is 90 to 400 parts by weight, preferably 140 to 3 parts by weight, per 100 parts by weight of the terpene resin.
00 parts by weight, but in order to achieve better adhesion to the base material when used as an allocating material, the amount of filler blended is smaller than that of asphalt (preferably). .

The present invention basically consists of the above three components, but in order to make the appearance more beautiful and smooth when the distribution material is supplied in the form of a sheet, 100 parts by weight of the terpene resin is added to the distribution material. A composition with excellent distribution performance can also be obtained by mixing 0.01 to 0.5 parts by weight of an antifoaming agent such as silicone oil, but at this time, terpene-based resin asphalt is melt-kneaded in advance. After that, by kneading other ingredients such as fillers, the dispersibility is improved (and a homogeneous composition can be obtained in a short time).

The melt mixing is carried out at a temperature of 80 to 200°C, preferably 100 to 160°C, under atmospheric pressure for 10 minutes to 1 hour.
Preferably, the mixing is carried out for 20 to 40 minutes using a mixing device such as a Brabender with a heating device, a mixing stirrer, a Nigu, an extruder or a roll.

The splittable composition obtained by the present invention has an excellent damping value (
It has the characteristics of being easy to handle as well as exhibiting excellent distribution performance), and is easy to handle without mixing hydrocarbon resin.
This is even more pronounced when the terpene resin is used alone.

The composition having vibration damping properties of the present invention may contain inorganic or organic fillers, flame retardants, pigments, stabilizers, etc. within a range that does not impair its vibration damping performance. Fillers that can be blended include valve powder, crushed paper, etc. Flame retardants include antimony oxide, halogenated aromatic compounds, halogenated aliphatic compounds, magnesium hydroxide, aluminum hydroxide, boron oxide, phosphate esters, Pigments include various known inorganic or organic pigments, such as red phosphorus, red phosphorus stabilized with aluminum hydroxide, ferrocene, ferrocene derivatives, iron acetylacetate, etc.; stabilizers include:
Examples include phenol-based and amine-based antioxidants, which are necessary during melt mixing, and known weather-resistant stabilizers, such as amine-based antioxidants, which are necessary when used as vibration damping materials, and these can be used alone or in combination. - can be blended as a mixture of

The vibration-damping composition of the present invention can be molded into sheet-like, block-like, or other shaped molded products, and can be applied to various machines, equipment, their housings, bridges, etc. that generate vibrations and noise due to rotation and reciprocating motion. It is used for structures, water and gas conduits, air conditioning ducts, and damping materials for various vehicles, but it is most suitable as a damping material for buildings, automobile panels, etc. .

The distribution material of the present invention is usually produced by kneading the above-mentioned composition in a per se known mixing machine such as a two-roll mixer equipped with a heating device, and then
It is supplied after being rolled onto a sheet with a thickness of 0.1 to 10 mm using a calendar roll and then cut into sheet pieces of approximately 1000 mm x 500 mm. Therefore, at this time, in order to smooth the sheet surface and improve its appearance, it is preferable to incorporate an antifoaming agent such as silicone oil as described above. Heat compression bonding using a heating blower, heat melting bonding in a non-pressure state, bonding with adhesives, etc. are used.
It can be used not only as a non-constrained type but also as a constrained type with a constrained layer attached to it, and can exhibit excellent distribution performance. In addition, since the vibration damping material of the present invention has excellent vibration damping performance, it is possible to exhibit sufficient vibration distribution effect even with an extremely thin sheet of 1 to 1.5 mm at most.
It is particularly suitable for use as a vibration damping material for panels that require weight reduction, and can achieve sufficient vibration damping effects with a usage amount of 174 to 1)5 compared to conventional asphalt-based damping materials. Obtainable.

As mentioned above, the damping material of the present invention has a high damping value over a wide range of 0°C to 60°C, and has a high damping value at frequencies of 50) 1
It has excellent allocation performance in the range of 1 kHz to 1 kHz.

The filler in the composition having vibration damping properties of the present invention increases the damping value in proportion to the amount blended, but as mentioned above, it also improves the adhesion followability, which is an important element as a vibration damping material. In order to do this, the amount of the asphalt is always smaller than that of asphalt (preferably).

(Effects of the Invention) According to the present invention, it is possible to obtain a splittable composition that has a further increased damping value in a wide temperature range of about 0°C to 60°C, compared to when petroleum resin is used alone. The cold resistance and flexibility are also improved, and the splitting material obtained from this composition has excellent adhesion followability to adapt to the uneven surface of the base material at high temperatures during use. This damping material can provide a high level of vibration damping with a relatively small amount of use compared to conventional damping materials, so it can contribute to reducing the weight of buildings, vehicles, etc.

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

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

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

Table 1 shows the maximum value (C/Cc1.) of the vibration damping ratio (damping value) for determining the damping performance of the damping material of the present invention, and the temperature at that time (T, . . . , l).

Adhesion followability: On the steel corrugated substrate shown in Fig. 1 (span between tops A + 30 mm, waveform inclination angle θ: 35°, waveform height B: 10mm, R of the top and bottom of the waveform: 8). , 20
Place the vibration damping sheet cut to 0mm x 40mm, and
Adhesion followability was observed after heating in an oven at 50° C. for 30 minutes. The state shown in Figure 2, that is, complete contact (distance (X) between the corrugated bottom and the sheet bottom is O)
+ (C)), with some voids at the bottom (X
is larger than O and 1 mm or less): (○), those with a considerable gap at the bottom (X is thicker than 1 mm (, 3 mm or less) = (Δ), those that do not soften (X is 3 mm or less) larger): expressed as (X).

A resin produced by cationic polymerization of terpene monomers such as α and β-pinene.

Resin A-1 (manufactured by Yasuhara Chemical Co., Ltd., trade name: rYS Resin) Hue 5 (Gardner, ASTM 0154-58
1 Softening point 100°C (ring and ball method) Resin A-2 (manufactured by Dainippon Ink and Chemicals Co., Ltd., trade name rNirezJ) Hue 4 (Gardner, ASTM 0154-581)
Softening point: 85°C (ring and ball method) Oil phase used in Examples and Comparative Examples The following petroleum resins were used in the Examples and Comparative Examples.

■ A product obtained by polymerizing a fraction mainly containing aromatic unsaturated hydrocarbons having 9 carbon atoms obtained during naphtha cracking, with a softening point (ring and ball method) of 120°C and a Cardner color number (melting method). ) 10, number average molecular weight 1000, bromine number 40, specific gravity 1.
Aromatic hydrocarbon resin having physical properties of
, this is called "petroleum resin B").

■ Obtained by polymerizing a fraction mainly containing aromatic unsaturated hydrocarbons with 9 carbon atoms obtained during naphtha decomposition, with a softening point (ring and ball method) of 100°C and a Gardner color number (melting method) of 1.
3. Aromatic hydrocarbon resin having physical properties of number average molecular weight 500, bromine number 40, and specific gravity 1.07 (manufactured by Mitsui Petrochemical Industries, Ltd., trade name [Mitsui Vetrogin #100J, referred to as 1 Petroleum Resin C]) ).

Blown asphalt modified with asphalt oil (penetration 20/30)
) Mica aspect ratio is 50 to 200, JIS Z8801
Examples 1 to 3, Comparative Examples 1 to 2 The formulations shown in Table 1 were 1) placed in a predetermined amount on two rolls made by Ashizawa ■ heated to 0°C. Add the resin component and asphalt and mix. When the kneaded ingredients begin to melt, mica is gradually added. When adding silicone oil,
Add it at the same time as mica. After about 15 minutes, the roll mixing is completed when the materials are sufficiently melted and kneaded and homogenized.

Next, the mixed wire was supplied to a calender roll while being cooled, and a vibration damping sheet having a thickness of 2 mm was created. The obtained distributed sheet was cut into a size of 32 mm x 300 mm and subjected to a physical property test.

The results are shown in Table 1.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a steel substrate for measuring the adhesion followability of a damping material in the present invention, and FIG. 2 is a sectional view showing evaluation of the adhesion followability of a damping material. ■--Sheet-like distribution material, 2... Steel substrate.

Claims (3)

[Claims] (1) 100 to 500 parts by weight of asphalt and 90 to 400 parts by weight of filler per 100 parts by weight of terpene resin
1. A composition having vibration-damping properties, characterized in that it contains parts by weight (however, the amount of filler blended is smaller than the amount of asphalt blended). (2) The composition according to claim (1), wherein the filler is mica. (3) A vibration damping material molded from the composition according to claim (1) or (2).