JP2583124B2 - Damping material composition and damping laminate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an amorphous polyolefin resin of an amorphous propylene / ethylene random copolymer, or grafting of the amorphous polyolefin resin with an unsaturated carboxylic acid or the like. The present invention relates to a vibration damping composition mainly composed of a modified material.

The present invention also relates to a vibration damping laminate obtained by laminating the vibration damping composition with a hard substrate such as a metal plate.

[Conventional technology]

In recent years, demands for a quiet environment have increased with the sophistication of life. For this reason, refrigerators, various home electric appliances such as washing machines and coolers, office equipment such as office automation equipment, automobiles, and the like, which have low noise and vibration are demanded. or,
Condominiums and office buildings are also strongly required to have soundproofing and vibration-proofing.

Conventionally, to prevent noise and vibration from household electrical equipment,
2. Description of the Related Art A vibration damping laminate in which a vibration damping material formed into a sheet shape of a vibration damping material composition and a hard base material such as a metal plate are laminated has been used.

Conventionally, as a damping material composition, resins having damping performance, for example, polyvinyl acetate, polyvinyl chloride, vinyl acetate / maleic acid diester copolymer, vinyl chloride / acrylic acid ester copolymer, ethylene Vinyl acetate copolymers, acrylonitrile / styrene copolymers, soft polyolefins, synthetic rubbers, polyisobutylene, cyclic olefin hydrocarbon resins, and the like, and compositions of these resins have been used.

These damping material compositions include a hot-melt type which is heated and softened to be laminated and adhered to a soft substrate such as a metal plate, and a solvent type which is dissolved in a solvent and applied to and laminated on a hard substrate.

Since the hot melt type does not use a solvent, it is superior in working environment and safety as compared with the solvent type. For this reason, in recent years, the hot melt type has come to be used more often.

[Problems to be solved by the present invention]

However, most of the hot melt types have a drawback of low vibration damping performance. Further, even a vibration damping material composition having excellent vibration damping performance at a high temperature was inferior in the vibration damping effect from a low temperature to a normal temperature.

Further, not only the hot melt type but also a crystalline resin is often used for the vibration damping composition. For this reason, when laminating with a hard base material such as a metal plate and cooling, the damping material may contract in volume. For this reason, in the conventional vibration damping laminate, there were problems that the vibration damping material was thinned and the adhesion to the hard base material was poor.

An object of the present invention is to provide a hot-met type vibration damping composition which exhibits good vibration damping performance in a wide temperature range of 0 to 60 ° C.

Another object of the present invention is to solve the problem of thinning of a vibration damping material and poor adhesion to a hard substrate when manufacturing a vibration damping laminate.

[Means for solving the problem]

The present invention relates to (1) (a) an amorphous propylene / ethylene random copolymer having a number average molecular weight in the range of 1,000 to 20,000 and an ethylene content of 8 to 30% by weight, and / or Or (b) an amorphous propylene / 1-butene random copolymer having a number average molecular weight in the range of 1,000 to 20,000 and a 1-butene content of 10 to 60% by weight. A damping material composition; and (2) a damping laminate obtained by laminating the above-described damping material composition on a hard substrate.

The vibration damping composition of the present invention can be used to block noise or vibration such as impact noise by inserting it between floors and floor supports or laying it under the floor in an apartment or office building. Used for

Further, as a sheet-shaped or block-shaped damping material, a vibration-damping laminate can be formed by laminating a hard base material such as a metal plate.

Specific examples of the configuration of the vibration damping laminate of the present invention include the following.

 Hard substrate / damping material Hard substrate / damping material / hard substrate Hard substrate / damping material / hard substrate / damping material Hard substrate / damping material / hard substrate / damping material / Hard base material.

Of these embodiments, sushi is most preferably used.

As the vibration damping composition of the present invention, amorphous propylene
An amorphous polyolefin resin such as an ethylene random copolymer, an amorphous propylene / 1-butene random copolymer, and a kneaded product of these random copolymers is used.

The above-mentioned amorphous polyolefin resin has a propylene content of 40% by weight or more. The ethylene content of the amorphous propylene / ethylene copolymer ranges from 8 to 30% by weight. Further, 1-butene copolymer of amorphous propylene and 1-butene
The butene content ranges from 10 to 60% by weight.

In the vibration damping composition of the present invention, the dynamic elastic modulus E '
Is preferably in the range of 1 × 10 ^{7 to} 5 × 10 ⁹ dyne / cm ^{2 in} the range of 0 to 60 ° C. from the viewpoint of the balance between the vibration damping performance and the shape retention.

Therefore, if the amorphous polyolefin resin has the above composition, the dynamic elastic modulus E ′ is 1 × 10 5 within the range of 0 to 60 ° C.
Since it falls within the range of ^{7 to} 5 × 10 ⁹ dyne / cm ² , it is suitable as a vibration damping composition.

The number average molecular weight of the amorphous polyolefin resin is 1,000
Must be in the range of ~ 20,000.

If the number average molecular weight is less than 1,000, it becomes too soft even at room temperature, so that the cohesive strength becomes weak. For this reason, there is a problem that the adhesion to the hard base material is likely to be defective.

When the number average molecular weight exceeds 20,000, the amorphous polyolefin resin becomes rubbery and the melt viscosity becomes high. For this reason, it becomes difficult to previously process the amorphous polyolefin resin into a thin sheet having a thickness of about 0.5 mm, or to cast the amorphous polyolefin resin on a hard base material with a doctor knife or the like.

The crystallinity of the amorphous polyolefin resin is preferably 20% or less, more preferably 10% or less. Crystallinity of 20
%, It is not preferable because the vibration damping performance is reduced and a problem of thinning occurs.

Amorphous polyolefin resins include, in addition to propylene, ethylene and 1-butene, 2-methylpropylene, 2-methyl-1-butene, 2-ethyl-1-butene, 3-methyl-1-butene, 1-pentene , 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-pentene, 3-ethyl-1- *
, 4-ethyl-1-pentene, 1-hexene and the like may be contained as a copolymer component.

In order to produce an amorphous polyolefin resin, for example, the following polymerization method can be used. It can be produced by a polymerization method such as introducing ethylene or 1-butene into liquefied propylene under a hydrogen atmosphere in the presence of a catalyst comprising titanium chloride supported on magnesium chloride and trialkylaluminum.

As the vibration damping composition of the present invention, an amorphous polyolefin resin graft-modified with an unsaturated carboxylic acid and / or an anhydride thereof, or a silane coupling agent can also be used.

Graft modification with an unsaturated carboxylic acid or a silane coupling agent can further improve the adhesion to a hard base.

The graft ratio of the amorphous polyolefin resin is 0.01 to 10
% By weight, especially in the range of 0.05 to 6% by weight. The graft modification can be performed by a method such as melt-kneading with an unsaturated carboxylic acid or the like in the presence of a radical initiator.

Examples of unsaturated carboxylic acids or anhydrides thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylic acid, and itaconic anhydride , Citraconic anhydride, hymic anhydride, bicyclo (2,2,2) oct-5-ene-2,3
-Dicarboxylic anhydride, 4-methylcyclohex-4-
Ene-1,2-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-
Octahydronaphthalene-2,3-dicarboxylic anhydride,
Bicyclo (2,2,1) oct-7-ene-2,3,5,6-tetracarboxylic acid-2,3,5,6-dianhydride, 7-oxabicyclo (2,2,1) hepta And -5-ene-2,3-dicarboxylic anhydride. Of these, maleic anhydride is particularly preferably used.

As the silane coupling agent, vinyl triethoxy silane, methacryloyloxy trimethoxy silane,
γ-methacryloyloxypropyltrimethoxysilane, methacryloyloxycyclohexyltrimethoxysilane, γ-methacryloyloxypropyltriacetyloxysilane, methacryloyloxytriethoxysilane, γ-methacryloyloxypropyltriethoxysilane and the like.

As the vibration damping composition of the present invention, a composition obtained by blending 5 to 100 parts by weight of a tackifier with 100 parts by weight of an amorphous polyolefin resin may be used.

Gum rosin, wood rosin,
Natural rosin such as tall oil, polymerized rosin, hydrogenated rosin, synthetic rosin such as maleated rosin, coumarone-indene resin, terpene resin, petroleum resin, phenol resin, and the like are used.

Further, inorganic fillers such as calcium carbonate, talc, mica, clay, silicic acid, gypsum, asbestos, carbon black, carbon fiber, metal powder, and metal fiber may be added.

In the vibration damping laminate of the present invention, the type of the metal plate used as the hard base material is not particularly limited, but iron, steel,
Alloy steel, high tensile steel, copper, stainless steel, aluminum,
Plates of aluminum alloy, phosphor bronze, bronze, brass, lead and the like are particularly preferred.

As the hard base material, in addition to a metal plate, a hard plastic or fiber-reinforced plastic plate or block, an inorganic material such as a particle board, general wood, a slate plate, a cement plate or a brick can be used.

The damping material laminated with the above composition is preferably a sheet-shaped or block-shaped damping material composition. However, not only the damping material composition formed in advance into a sheet shape or a block shape, but also the damping material composition may be melted and poured between hard base materials.

Therefore, the vibration damping laminate of the present invention can be manufactured, for example, as follows.

The above-mentioned damping composition is heated and melted, cast on a hard base material, and formed into a damping material. A method of stacking another hard base material on top of this, heating and pressing the base material, or the like is possible. or,
The above-described damping material composition is processed into a sheet-shaped damping material having a thickness of about 0.5 mm in advance, and processed into a sheet-shaped damping material having a thickness of about 0.5 mm. It can also be produced by a method of heating and crimping by sandwiching between them.

〔Example〕

 Hereinafter, examples of the present invention will be described.

Example 1 As a vibration damping material composition, an amorphous propylene / ethylene random copolymer (Rexene, Rextac B2A80, number average molecular weight 7,400 (measured at 135 ° C. using ortho-dichlorobenzene (ODCB) as a solvent)), ethylene content 10% by weight). Heat this amorphous propylene / ethylene copolymer,
Melted and degreased cold rolled steel sheet ST using a doctor knife
It was cast on a CC (thickness 0.5 mm, width 20 mm, length 270 mm) to form a vibration damping material. The same cold-rolled steel plate STCC is further laminated on top of it,
Heat bonding was performed at 0 ° C and 5 kg / cm ² for 1 minute to produce a vibration-damping laminate having a thickness of 0.5 mm / 0.2 mm / 0.5 mm of cold-rolled steel sheet / damping material / cold-rolled steel sheet. .

The vibration damping performance of the vibration damping laminate was evaluated by measuring the loss coefficient η while changing the temperature by the resonance method of mechanical impedance. A spectrum analyzer type 2032 manufactured by Brüel & Kjær Company was used as a measuring device. The measurement temperature range was 0 to 90 ° C. Data shows values at 500 Hz.

The dynamic viscoelastic coefficient E ′ of the vibration damping composition was measured using a Leo Vibron Model-IIC manufactured by Toyo Baldwin.

 The results are shown in Table 1 and FIG.

[Example 2] Rextac B5A80 (manufactured by Rexene, amorphous propylene / ethylene random copolymer, number average molecular weight) was added to the damping material composition.
A vibration damping laminate was prepared in the same manner as in Example 1, except that 7,300 (the measuring method and the measuring conditions were the same as in Example 1) and the ethylene content was 20% by weight. The dynamic viscoelastic coefficient E 'of the material composition was measured.

 The results are shown in Table 1 and FIG.

[Example 3] As a vibration damping material composition, an amorphous propylene / 1-butene random copolymer (Rexene, RextacE5, number average molecular weight 9,000 (the measurement method and measurement conditions are the same as in Example 1), 1
-Butene content of 40% by weight) was used to prepare a damping laminate in the same manner as in Example 1, and the loss coefficient η and the dynamic viscoelastic coefficient E ′ of the damping material composition were measured. .

 The results are shown in Table 1 and FIG.

Example 4 Amorphous propylene / ethylene random copolymer (Rexe
ne Corporation, Rextac B2A80) 50% by weight and a tackifier (Mitsui Petrochemical, Hiretsu T1115) 50% by weight were kneaded with a Brabender to obtain a blend.

This blend was cast on a cold-rolled steel sheet in the same manner as in Example 1. Further, another cold-rolled steel sheet was laminated and heated and pressed to produce a vibration-damping laminated body.

The loss coefficient η of the damping laminate and the dynamic viscoelastic coefficient E ′ of the damping material composition were measured in the same manner as in Example 1.

 The results are shown in Table 1 and FIG.

Example 5 Amorphous propylene / ethylene random copolymer (Rexe
100 parts by weight of Rextac B2A80 (manufactured by ne company), 1 part by weight of maleic anhydride, and 0.002 part by weight of lauroyl peroxide as a radical initiator were melt-kneaded to obtain a maleic anhydride graft copolymer.

Using the maleic anhydride graft copolymer as a vibration damping material, a damping laminate was prepared in the same manner as in Example 1, and the loss coefficient η of the damping laminate and the dynamic viscosity of the damping material composition were measured. The elastic modulus E 'was measured.

 The results are shown in Table 1.

[Comparative Example 1] A damping laminate was prepared in the same manner as in Example 1 except that a maleated crystalline polypropylene resin (Block polypropylene J701H manufactured by Ube Industries) was used as a damping material, and a loss coefficient was obtained. η and the dynamic viscoelastic coefficient E ′ of the resin layer were measured.

 The results are shown in Table 1 and FIG.

In the damping laminates of Examples 1 to 5, the dynamic viscoelastic coefficient E ′ of the damping material composition was 2.1 × 10 ^{8 to} 4.9 × 1 at 0 ° C.
It is in the range of ⁰⁹ . At 60 ° C., the range is 2.3 to 10 ⁷ to 8 × 10 ⁷ . Therefore, the preferred range of the dynamic viscoelastic coefficient is 1 × 10 ^{7 to} 5 at both 0 ° C. and 60 ° C.
It is within × 10 ⁹ dyne / cm ² .

When the loss coefficient η of the vibration damping laminate is measured by changing the measurement temperature under the conditions of the present example, the temperature range of η ≧ 0.1 is:
The temperature range in which the vibration damping performance of the vibration damping laminate is good. In the vibration damping laminates of Examples 1 to 5, this temperature range was 27
~ 60 ° C ~ 0 ° C ~ 60 ° C, widely distributed around room temperature.

This indicates that the vibration damping laminate of the present invention has excellent vibration damping performance especially at around room temperature.

(Effect of the present invention)

The vibration damping composition of the present invention contains an amorphous polyolefin resin having a specific molecular weight or a composition thereof as a main component. For this reason, it is excellent in vibration damping performance and shape retention near normal temperature. Therefore, it is suitable for use in various vibration damping materials and sound insulation materials.

Further, the vibration damping composition has a low melt viscosity. Therefore, it is easy to heat and melt and cast on a hard substrate, or to form a sheet.

Further, since the vibration damping composition is an amorphous resin, the vibration damping material does not become thin or does not have poor adhesion to the metal plate during the production of the vibration damping laminate. .

[Brief description of the drawings]

FIG. 1 shows the relationship between the loss coefficient η and the temperature of the damping laminates of Examples 1 to 5 and Comparative Example 1.

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Claims (6)

(57) [Claims] (A) an amorphous propylene / ethylene random copolymer having a number average molecular weight in the range of 1,000 to 20,000 and an ethylene content of 8 to 30% by weight; and / or (B) an amorphous propylene / 1-butene random copolymer having a number average molecular weight in the range of 1,000 to 20,000 and a 1-butene content of 10 to 60% by weight; A vibration material composition. 2. An amorphous propylene / ethylene random copolymer and / or (b) an amorphous propylene / 1-
2. The vibration damping composition according to claim 1, wherein the butene random copolymer is formed of an unsaturated carboxylic acid and / or an anhydride thereof. 3. An amorphous propylene / ethylene random copolymer and / or (b) an amorphous propylene / 1-
2. The vibration damping composition according to claim 1, wherein the butene random copolymer is graft-modified with an unsaturated silane coupling agent. 4. (a) The vibration damping composition according to claim 1, 2 or 3, 100 parts by weight (b) tackifier 5-100 parts by weight A vibration damping composition comprising: 5. Claims 1, 2, 3 and 4,
Alternatively, a vibration damping laminate obtained by laminating the vibration damping material composition according to claim 4 on a hard substrate. 6. The vibration damping laminate according to claim 5, wherein the hard base is a metal plate.