JPH0613629B2 - Damping material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vibration damping material, and more particularly to a new vibration damping material that has good adhesion to a metal and excellent vibration damping performance at high temperatures.

[Prior Art] Conventionally, in order to suppress or prevent noise and vibration generated from various mechanical devices, electric devices, structures, and the like, a metal plate using a viscoelastic resin or resin composition as a damping material. There has been proposed or put into practical use a vibration-damping composite laminate in which the vibration-damping performance is expressed by utilizing the internal friction due to the shearing deformation of the vibration-damping material, which is laminated between the substrates. An example of such a damping material composition is disclosed in JP-A-54
-43251 or JP-A-54-43252 describes a composition containing polyibutylene as a main component and a diene hydrocarbon polymer or cyclic olefin polymer and an inorganic filler. . Japanese Unexamined Patent Publication (Kokai) No. 57-34949 describes a damping material composed of an ethylene / vinyl acetate copolymer. JP-A-59-80454 describes a composition comprising a modified product of highly crystalline polyolefin and an amorphous polymer. Japanese Unexamined Patent Publication No. 61-89842 discloses a damping material made of polyester or polyester having specific properties and polyolefin.

Further, regarding a composition comprising a polyester and a modified polyolefin, JP-B-59-28223 discloses a composition in which a polyester is a matrix phase and a modified polyolefin is a domain phase, and is disclosed in JP-B-57-54058. Describes a composition in which a modified polyolefin is blended at a ratio of 1/10 to 4 times that of polyester. Further, JP-A-57-203546 describes a metal body coated with a resin composition of a polyolefin which may be modified and a polyester which may be amorphous.

[Problems of conventional technology]

Among the above-mentioned conventional techniques, those disclosed in JP-A-54-43251, JP-A-54-43252, and JP-A-57-34949 have insufficient vibration damping properties, especially at high temperatures. There is a problem in that it cannot be used as a high temperature damping material around the engine, for example. The materials disclosed in JP-A-59-80545 have insufficient adhesion to metals and poor heat resistance. The one disclosed in Japanese Patent Laid-Open No. 61-89842 is blended with polyolefin, which is copolymerized with glycidyl methacrylate, in order to improve adhesiveness with a metal, to a non-crystalline polyester having relatively large elongation and softness. Although it is superior to the conventional damping material in the high temperature range, the damping performance in the temperature range of 80 to 100 ° C required especially as the damping material around the engine is sufficient. However, further improvement is desired. Further, the composition of polyester and modified polyolefin described in JP-B-59-28223, JP-B-57-54058 or JP-A-57-203546 is a crystalline polyester, assuming amorphous polyester. Not mentioned, or the composition of the matrix phase / domain phase in the resin composition is different, and not only the damping material application is not described, but also the damping material application is assumed from the purpose, action, and effect. It cannot be done.

[Problems to be Solved by the Invention] An object of the present invention is to provide a vibration damping material having excellent vibration damping performance, particularly in a high temperature range. Another object of the present invention is to provide a vibration damping material having excellent adhesion to different kinds of base materials such as metals. Other objects of the present invention will be apparent from the description of the specification given below.

[Means for solving problems]

That is, the present invention comprises a composition comprising a matrix phase of a low crystalline polyolefin (A) modified with an α, β-unsaturated carboxylic acid and a domain phase of an amorphous polyester (B), and a modified low crystalline polyolefin. (A) is 35-60wt
%, The amorphous polyester (B) is 40 to 65 wt%, and in a preferred embodiment thereof, the resin composition is in the form of a composite laminate in which a metal is laminated. The material is provided.

[Work]

The resin composition constituting the vibration damping material of the present invention is a low crystalline polyolefin modified with α, β-unsaturated carboxylic acids.
(A) and an amorphous polyester (B), and in the resin composition, modified low crystalline polyolefin
(A) is the matrix phase and the amorphous polyester (B) is the domain phase. If the resin that constitutes the matrix phase and the domain phase is the reverse of the above, sufficient adhesive strength to the steel sheet cannot be obtained under the adhesive temperature condition that does not particularly deteriorate the steel sheet, and due to the moisture absorption characteristics of polyester. There is also a problem of poor water-resistant adhesive durability performance. Further, when a modified crystalline polyolefin is used as the modified polyolefin, there is a problem that the vibration damping performance is extremely deteriorated in a blend system with an amorphous polyester.

In the present invention, the modified low-crystalline polyolefin, which is a base, is a polyolefin having a crystallinity of 20% or less, which is ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1- Penten, 1-octene,
Of the α-olefins such as 1-decene, homopolymers or interpolymers, ethylene / 1-butene or ethylene / propylene random copolymers are particularly preferable.

Α used to modify the low crystalline polyolefin
Examples of β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, and itaconic anhydride, with maleic acid and maleic anhydride being preferred.

The modified low crystalline polyolefin (A) has the above α, β
Obtained by grafting unsaturated carboxylic acids onto low crystalline polyolefin, usually 0.05 to 2 parts by weight, especially 0.3 to 0.
Use 6 parts by weight grafted.

Examples of the amorphous polyester (B) include ethylene glycol, propylene glycol, 1,4-butanediol,
Aliphatic glycols such as neopentyl glycol and hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4- (vidroxyethoxy)
Aromatic dihydroxy compounds such as benzene, or dihydroxy compound units selected from two or more of these, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, oxalic acid, succinic acid, adipic acid , A sebacic acid, an aliphatic dicarboxylic acid such as undecadicarboxylic acid, an alicyclic dicarboxylic acid such as hexahydroterephthalic acid, or a polyester formed from a dicarboxylic acid unit selected from two or more of these. The crystalline resin may be modified with a small amount of trihydroxy or higher polyhydroxy compound such as triol or tricarboxylic acid or polycarboxylic acid as long as it exhibits thermoplasticity. As these amorphous polyesters, specifically, 15 to 100 mol% of the dicarboxylic acid component, preferably 50 to 100 mol%
Is an isophthalic acid and the balance is a dicarboxylic acid component consisting of other dicarboxylic acid components such as terephthalic acid, and an amorphous isophthalate polymer consisting of a dihydroxy compound component such as ethylene glycol, a dicarboxylic acid component consisting of terephthalic acid, and dihydroxy An amorphous terephthalate copolymer in which 15 to 50 mol% of the compound component is cyclohexanedimethanol and the balance is another dihydroxy compound component such as ethylene glycol can be used.

Among the amorphous isophthalate polymers, the balance of the dicarboxylic acid component is 5 to 90 mol% of terephthalic acid and the dihydroxy compound, and further 10 to 15 mol% is 1,3-bis (2-hydroxyethoxy) benzene. Alternatively, the isophthalate polymer composed of 1,4-bis (2-hydroxyethoxy) benzene and 10 to 95 mol%, and further 75 to 90 mol% of ethylene glycol has a large vibration damping property in the same blend amount. Is preferred.

Amorphous in the present invention is a resin that does not cause devitrification due to crystallization when left in an atmosphere of 190 ° C. for 3 hours or more, and has no clear crystallization or crystal melting peak in DSC measurement. It is a resin. Tg is a value obtained from the transition point of latent heat at the time of temperature increase by DSC at a temperature increase rate of 10 ° C./min.

The molecular weight of the amorphous polyester (B) used in the present invention is not particularly limited as long as it does not impair the film moldability of the composition, but is usually o-chlorophenol at 25 ° C. I.
V. is 0.6 dl / g or more, preferably 0.8 to 0.9 dl / g.

As the amorphous polyester (B) as described above
As an easily available commercial product, Eastman Co.
KODAR, a product of Datsk  PETG or PCTA
However, the maximum temperature of the loss factor is 105 ° C and
There is some problem that it is as high as 110 ° C.

In the present invention, as described above, the modified low crystalline polyolefin (A) uses a resin composition in which the matrix phase and the amorphous polyester (B) become the domain phase, but since such a phase structure is obtained. (A) is 35-60 wt
%, (B) is mixed in the range of 40 to 65 wt%.
To confirm that the phase structure is as described above, it is possible to observe the molten Brent composition of both resins with an electron microscope.

The damping material of the present invention can be used in the form of a composite laminate with a metal plate, or in the form of a composite composition.

A method of using the damping material of the present invention as a damping material composed of a composite laminate will be described below. The composite laminate for damping material has at least an outer layer made of a metal, and at least one of the intermediate layers.
The layer is a damping material made of the above composition, and the metal layer may be formed not only in the outer layer but also in the intermediate layer. The composition of the composite laminate is as follows. The thing of a structure can be illustrated.

(I) metal / composition (ii) metal / composition / metal (iii) metal / composition / metal / composition (iv) metal / composition / metal / composition / metal Of these, the composite laminate having the three-layer structure (ii) is particularly preferably used. The structure of the composite laminate can be used as a plate, a cylinder, a prism, or any other shape of structure.

Examples of the metal forming the composite laminate include iron, steel, copper, aluminum, stainless steel, brass and the like. The thickness of the metal is arbitrary, but is usually in the range of 0.1 to 2 mm, preferably 0.2 to 0.4 mm.

If necessary, an inorganic filler may be added to the damping material. Specific examples include graphite, mica, titanium oxide, zinc oxide, clay, calcium carbonate, magnesium carbonate, carbon black and the like. You can

The thickness of the composition layer to be the intermediate layer is arbitrary, but is usually 0.
It is in the range of 02 to 3 mm, preferably 0.03 to 0.15 mm.

A conventionally known method can be adopted as a method for producing the composite laminated plate in which the damping material is a metal plate or an intermediate layer of a plurality of metal plates.

〔The invention's effect〕

According to the present invention, it is possible to provide a vibration damping material having excellent vibration damping performance, particularly vibration damping performance in a high temperature region, as well as a vibration damping material having excellent adhesion to a metal. Moreover, as shown in Examples described later, it exhibits vibration damping performance in a wider temperature range than that using only the amorphous polyester. Therefore, it is useful as an engine peripheral part such as for engine / oil pan and cylinder head cover.

〔Example〕

Hereinafter, the contents of the present invention will be described with reference to preferred examples, but the present invention is not limited to these examples unless otherwise specified.

Example 1 As an unsaturated carboxylic acid-modified low crystalline polyolefin (A-1) to be a matrix layer, 100 parts by weight of an ethylene / 1-butene random copolymer having an ethylene content of 90 mol% was added to 0.015 part by weight of acetone and anhydrous. A mixed solution consisting of 0.5 part by weight of maleic acid was added dropwise using a Henschel mixer, and then granulated at 240 ° C. with a 40 mmφ extruder to obtain a crystallinity of 15%, MFR 3 g / 10 min, maleic anhydride. Graft amount
0.35% by weight of maleic anhydride-grafted ethylene / 1-butene random copolymer was obtained.

As the amorphous polyester (B-1) for the domain layer, isophthalic acid / terephthalic acid / ethylene glycol / 1,3-bis (2-hydroxyethoxy) benzene / trihydroxymethylpropane 90/10/85 / 15 / 0.3
Copolymerization with a molar composition was performed to obtain an amorphous polyester with IV = 0.85 dl / g.

The above resins A-1 and B-1 were mixed in equal weight ratios and granulated in a 40 mmφ extruder at 230 ° C., and then a film of 70 μm at 230 ° C. using a 300 mm width T die equipped with a 30 mmφ extruder. Got

This film was sandwiched between two 0.8 mm thick low carbon steel sheets that had been subjected to degreasing with an alkaline detergent, press-molded at 190 ° C for 10 minutes, and then subjected to a T-peel test of 25 mm width at 100 mm / m.
It went at the speed of in.

Example 2 As the matrix layer resin (A-2), an ethylene / propylene random copolymer having an ethylene content of 80 mol% was grafted with maleic anhydride in the same manner as in Example 1 to obtain a crystallinity of 4.
%, MFR 0.5g / 10min, maleic anhydride graft amount 0.35
A wt% maleic anhydride grafted ethylene / propylene random copolymer was obtained.

The above resins A-2 and B-1 were mixed in the same weight ratio, and the T peel strength was determined by the same procedure as in Example 1.

Comparative Example 1 As a matrix resin (A-3), ethylene glycidyl was used.
Lumethacrylate / vinyl acetate copolymer (Sumitomo Chemical Industries, Ltd.
Bond Bond Fast 2B) and mixed with B-1 in Example 1
I went as well.

Comparative Example 2 Only the resin B-1 of Example 1 was similarly used as a film to determine the T peel strength.

Comparative Example 3 Resin B-1 of Comparative Example 2 was produced by Eastman Kotsk Kodar
The PET peeling strength was changed to PET G 6763 and the T peel strength was determined.

Table 1 shows the T-type peel strength test results of Examples 1 and 2 and Comparative Examples 1 to 3 described above.

As can be seen from the results, the present invention can achieve the generally required steel / resin / steel T-peel strength of 10 kg / 25 mm or more as a damping steel plate.

Examples 3 to 6 and Comparative Example 4 By the same procedure as in Example 1, a film in which the mixing weight ratio of the resins A-1 and B-1 was changed as shown in Table 2 was obtained, and further a maleic anhydride-modified high-density polyethylene was used. A three-layer film sandwiched between two 15 μ films was used to prepare a vibration-damping steel plate in the same manner as in Example 1, and the T peel strength and the vibration loss coefficient η by the cantilever resonance point vibration damping method were measured.

Comparative Example 5 The matrix layer of Example 4 was changed to a mixture of resin A-1 and maleic anhydride-modified high-density polyethylene having a crystallinity of 60% in a weight ratio of 7: 3, and the same procedure as in Example 4 was evaluated. .

Table 2 shows the results of the T peel strength and the loss coefficient η of Examples 3 to 6 and Comparative Examples 1, 2, 4, and 5 described above.

From these results, T-type peel strength of 10kg / 25mm or more, which is generally required for damping steel sheets, and loss factor η, which is required for automotive engine peripheral applications (oil pans, cylinder covers, etc.), is high in the range of 80-100 ° C ( At least in part η
It can be seen that the present invention can simultaneously achieve both of the above conditions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 67/00 LPB 8933-4J F16F 9/30 Z 9240-3J

Claims (6)

[Claims] 1. A modified low crystalline polyolefin comprising a composition comprising a low crystalline polyolefin (A) modified with an α, β-unsaturated carboxylic acid as a matrix phase and an amorphous polyester (B) as a domain phase. (A) is 35-60wt
%, The amorphous polyester (B) is 40 to 65 wt%, a vibration damping material. 2. The crystallinity of the low crystalline polyolefin is 20%.
The damping material according to claim 1, which is as follows. 3. The vibration damping material according to claim 1 or 2, wherein the α, β-unsaturated carboxylic acid is maleic acid or maleic anhydride. 4. A dicarboxylic acid component of an amorphous polyester
15-100 mol% isophthalic acid, balance terephthalic acid,
5 to 90 mol% of the dihydroxy compound component is 1,3-bis (2-
The vibration damping material according to any one of claims 1 to 3, wherein hydroxyethoxy) benzene and / or 1,4-bis (2-hydroxyethoxy) benzene and the balance is ethylene glycol. 5. The first aspect of the present invention, which is laminated with a metal.
The damping material according to any one of items 4 to 4. 6. The vibration damping material according to any one of claims 1 to 5, which is used for an engine oil pan or a cylinder head cover.