JPH0781053B2 - Resin composition for damping material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition for vibration damping materials having good adhesiveness to different materials such as metals and a composite laminate thereof, and more specifically, to a durable adhesiveness. TECHNICAL FIELD The present invention relates to a resin composition for a vibration damping material which is excellent and has excellent vibration damping performance in a high temperature region, and a composite laminate thereof.

[Conventional technology]

Regarding the composition comprising a polyester and a modified polyolefin, a composition in which the polyester matrix is a matrix phase and the modified polyolefin is a domain phase is described in JP-B-59-28223, and JP-B-57-54058 discloses. A composition is described in which the modified polyolefin is blended in a ratio of 1/10 to 4 times that of polyester. Furthermore, JP-A-57-203546 discloses a metal body coated with a resin composition of a polyolefin which may be modified and a polyester which may be amorphous. JP-A-58-63742 describes a composition comprising a polyester, a modified polyolefin and an inorganic filler.

Further, regarding a composition containing a silane coupling agent, Japanese Patent Application Laid-Open No. 60-253536 discloses a vibration-damping agent having a viscoelastic substance as an intermediate layer, which may contain a filler treated with the silane coupling agent. For example, JP-A-55-31838 describes a Sangerichi steel plate having a molten mixture of a polyolefin, a silane coupling agent, a filler and a radical generator as an intermediate layer.

[Problems of conventional technology]

Among the above-mentioned conventional techniques, JP-B-59-28223 is intended to improve impact properties of polyester, and the matrix phase and the domain phase are different from the composition constituting the damping material of the present invention. Moreover, as a matter of course, only the crystalline polyester is disclosed. Moreover, there is no description about the blending of the silane coupling agent, and no description or suggestion about the adhesion to different materials such as metals or the vibration damping performance. Japanese Examined Patent Publication (Kokoku) No. 57-54058 also aims to improve impact properties, and thus all polyesters disclosed are crystalline. Moreover, as in the above-mentioned publication, there is no suggestion about the compounding of the silane coupling agent, the adhesion with the metal, and the vibration damping performance. JP-A-57-20
No. 3,546, there is no suggestion about the composition of the silane coupling agent and the vibration damping performance. JP-A-58-63742 aims to improve impact properties, and the polyethylene disclosed therein is crystalline and also contains a large amount of inorganic filler. And, of course, there is no suggestion about the compounding of the silane coupling agent, the adhesion to the metal, and the vibration damping performance. In JP-A-60-253536, there is no description about amorphous polyester and modified low crystalline polyolefin,
In addition, the silane coupling agent is used to improve the dispersibility when blending the filler, and therefore, both the filler and the silane coupling agent are blended in a large amount. JP-A-55-31838 discloses that a silane coupling agent is used for graft modification of a base polyolefin, as can be seen from the fact that a radical generator is used.
Of course, there is no suggestion about amorphous polyester or modified low crystalline polyolefin.

It is difficult to say that any of the conventional compositions described above is satisfactory in terms of the balance with the adhesiveness to different materials and the damping performance, especially the damping performance in the high temperature range.

[Problems to be solved by the invention]

An object of the present invention is to provide a resin composition for a vibration damping material, which can suitably provide a vibration damping material composed of a metal / resin / metal having good adhesiveness to a metal, that is, initial adhesiveness and durable adhesiveness. It is in. Another object of the present invention is to provide a composite laminate for a vibration damping material (hereinafter, simply referred to as a "damping material") using the resin composition for a vibration damping material, which has excellent vibration damping performance in a high temperature region. There is). Still another object 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 low crystalline polyolefin (A) modified with an unsaturated carboxylic acid, an amorphous polyester (B), a silane coupling agent (C) and an inorganic filler (D), A) is 30-60wt%,
40 to 70 wt% of (B), 0.05 to 4 parts by weight of (C) and 0.5 to 4 parts by weight of (D) are added per 100 parts by weight of the total amount of (A) and (B), Further, (A) is a matrix phase and (B) is a domain phase, and a vibration damping material comprising a resin composition for vibration damping material and a laminate of the resin composition and a metal.

[Work]

The low crystalline polyolefin, which is a base of the modified low crystalline polyolefin which is one component of the resin composition constituting the vibration damping material of the present invention, is a polyolefin having a crystallinity of 20% or less, and ethylene, propylene, -Butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-
Examples thereof include homopolymers or intercopolymers of α-olefin such as octene and 1-decene.

Fatigue used to modify the low crystalline folio olefin.
Examples of the carboxylic acids include acrylic acid and meta.
Acrylic acid, α-ethylacrylic acid, maleic acid, fumar
Acid, itaconic acid, citraconic acid, tetrahydrophthal
Acid, Methyltetrahydrophthalic acid, Enzocis-bisic
[2.2.1] Hept-5-ene-2,3-dicarboxylic acid (Na
Dickic acid ), Methyl-endocis-bicyclo (2.2.
1] Hept-5-ene-2,3-dicarboxylic acid (methyl nadi
Tuctric acid ), An unsaturated carboxylic acid such as
Acid halide of acid, amide, imide, acid anhydride, ester
And unsaturated carboxylic acid derivatives such as
Contains maleenyl chloride, maleimide, maleic anhydride, no
Water citraconic acid, monomethyl maleate, di maleate
Methyl etc. are illustrated. Among these, unsaturated Zika
Rubic acid or its acid anhydride is preferred, and maleic acid is particularly preferred.
In-acid, nadic acid or their anhydrides are preferred.
It

The modified low crystalline polyolefin (A) was obtained by grafting the above-mentioned unsaturated carboxylic acids onto the low crystalline polyolefin, and was usually 0.3 to 0.6 part by weight per 100 parts by weight of the low crystalline polyolefin. The thing is used as a main component.

Examples of the amorphous polyester (B) include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexamethylene glycol and other aliphatic glycols, cyclohexanedimethanol and other alicyclic glycols, and bisphenols. Aromatic dihydroxy compounds such as 1,3-bis (2-hydroxyethoxy) benzene and 1,4-bis (hydroxyethoxy) benzene, or dihydroxy compound units selected from two or more of these, and terephthalic acid and isophthalic acid , 2,6-
Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, aliphatic carboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid, or these 2
It is an amorphous resin among polyesters formed from dicarboxylic acid units selected from one or more kinds, and as long as it has thermoplasticity, a small amount of triol or tricarboxylic acid such as 3
It may be modified with a polyhydroxy compound having a valency or more or a polycarboxylic acid. As these amorphous polyesters, specifically, a dicarboxylic acid component consisting of 15 to 100 mol% of the dicarboxylic acid component, preferably 50 to 100 mol% of isophthalic acid and the balance of other dicarboxylic acid component such as terephthalic acid. And an amorphous isophthalate polymer composed of a dihydroxy compound component such as ethylene glycol, a dicarboxylic acid component composed of terephthalic acid, 15 to 50 mol% of the dihydroxy compound component is cyclohexanedimethanol, and the balance is ethylene glycol or the like. And an amorphous terephthalate copolymer composed of the dihydroxy compound component of

Among the amorphous isophthalate polymers, the balance of the dicarboxylic acid component is 5 to 90 mol% of terephthalic acid and dihydroxy compound, and further 10 to 15 mol% is 1,3-bis (2-hydroxyethoxy) benzene. Alternatively, 1,4-bis (2-hydroxyethoxy) benzene and an isophthalate polymer composed of 10 to 95 mol%, and further 75 to 90 mol% of ethylene glycol in the same blend amount.
It is preferable because it has a large vibration damping property at 80 to 100 ° C.

The glass transition temperature (Tg) of these amorphous polyesters (B) exists in various ranges, but it is usually about 40-100.
℃, preferably 50-60 ℃.

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 a clear crystallization or crystal melting peak in DSC measurement. There is no resin. Also, the Tg of the amorphous polyester resin (B) was determined by DSC to raise the temperature by 10 ° C / mi.
It is a value obtained from the transition point of latent heat at the time of temperature rise in n.

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 the IV at o-chlorophenol at 25 ° C. is usually 0.6 dl / g or more, It is preferably in the range of 0.8 to 0.9 dl / g.

As the amorphous polyester (B) as described above,
As a commercially available brand that can be easily obtained,
KODAR, a product of Kodak Company  PETG or PCTA etc.
is there.

The silane coupling agent (C) is the adhesiveness of the composition comprising the modified low crystalline polyolefin (A) and the amorphous polyester (B), that is, the initial adhesiveness at the time of high-speed lamination with a metal or oil or water. It is blended in order to improve the durable adhesiveness which does not reduce the adhesive strength even if it is kept in contact for a long time. Separately, by adding the silane coupling agent (C), the vibration loss coefficient η in the same mixing ratio of (A) and (B) is higher than that in the case of not adding the silane coupling agent. It also has the unexpected effect of increasing the vibration damping performance.

As the silane coupling agent, various known ones can be applied, but among them, γ-glycidoxypropyltrimethoxysilane or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferable, and especially the former Is preferred. However, silane coupling agents other than these may be used, and specific examples of such silane coupling agents are described in "Crosslinking Agent Handbook" No. 558 published by Taiseisha.
Pp. 561.

The main performance as a damping material is these (A) to (C).
Although it is controlled by the ratio of each component of (3), it is difficult to granulate when it is composed of only three components (A) to (C). That is, normally, (A) to (C) are premixed by a Henschel mixer or a tumble mixer and then granulated by a granulator. At this time, if there are only three components, prologking is likely to occur in the granulator hopper, and the raw material is Not properly supplied to the granulator. In order to prevent such a phenomenon, in the present invention, an inorganic filler (D) is added in addition to the above three components.

As the inorganic filler, known ones such as talc, silica, calcium carbonate, clay and mica can be used, and when applied, when the vibration damping material is obtained in a film shape, the particle size and particle size distribution are selected so as not to impair the film forming property. Is appropriately selected.

The resin composition is a blend of the components (A) to (D), and the proportion of each component is (A) 30 to 60 wt%, preferably
40 to 50 wt% (B) is 40 to 70 wt%, preferably 50 to 60 wt%,
(C) is 0.05 per 100 parts by weight of the total amount of (A) and (B).
-4 parts by weight, preferably 1 to 2 parts by weight (D) is 0.5 to 4 parts by weight, preferably 1 to 2 parts by weight. further,
In the composition, the low crystalline polyolefin (A) should be the matrix phase and the amorphous polyester (B) should be the domain phase. If the resin that constitutes the matrix phase and the domain phase is the reverse of the above, long-term water resistant adhesive durability cannot be expected due to the water absorption of polyester, and the thin film forming property is not expected. Also causes problems.

Further, as the modified polyolefin, a modified product of low crystalline polyolefin is used as described above, but if a modified product of highly crystalline polyolefin is used, a silane coupling agent may be added in a blend system with an amorphous polyester. Even if used together, it cannot exhibit sufficient adhesive strength,
Even if laminated with a metal, interfacial peeling is likely to occur, and the moldability tends to be poor. On the other hand, if the proportion of (A) is too small in the above proportion, the composition of the matrix phase and the domain phase will be reversed, resulting in a composition with poor adhesiveness and processability. . If the proportion of (C) is too small, the water-resistant adhesiveness is not improved and the vibration damping performance is not improved. On the other hand, if the amount is too large, it becomes too hard and the vibration damping performance deteriorates, and the workability tends to deteriorate.
Further, if the amount of (D) is too large or too small, the moldability during granulation or film forming to form a resin layer of the vibration damping material will deteriorate.

It is possible to confirm that the phase structure is as described above by observing with an electron microscope.

In order to obtain the resin composition that constitutes the inner layer of the vibration damping material of the present invention, for example, a method of melt blending (A), (B), (C) and (D) at the same time, (B), (C) and There is a method in which (D) is melt-blended, and then (A) is added and further melt-blended.

Other resins may be added to the above resin composition within a range that does not significantly impair its properties. Examples of such a resin include ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid salt copolymer, and ethylene / (meth) acrylic acid ester copolymer. Of course, it will be obvious to those skilled in the art to use known resins other than these.

The above resin composition has a large loss coefficient η at 80 ° C. or higher, especially between 80 ° C. and 100 ° C., and is preferably used as a resin layer of a vibration damping material in the engine peripheral portion such as an oil pan.

A method of using the resin composition for a vibration damping material of the present invention as a vibration damping material composed of a composite laminate will be described below. The composite laminate for vibration damping material is such that at least the outer layer is made of metal and at least one of the intermediate layers is made of the composition, and the metal layer is not only the outer layer but also the intermediate layer.
It doesn't matter if the layers are formed. Examples of the structure of the composite laminate include the following structures.

(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. Further, the thickness of the composition layer is also optional, usually 0.02 ~ 3m
m, preferably in the range of 0.03 to 0.15 mm.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a vibration damping material having excellent vibration damping performance, particularly in a high temperature range, and also to have excellent adhesiveness with a metal constituting the vibration damping material, that is, initial adhesiveness and water resistant adhesiveness. A composition can be provided.

〔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.

Examples 1 to 4 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 a crystallinity of 17% and an ethylene content of 90 mol%. In addition, after dropwise mixing a mixed solution consisting of 0.015 parts by weight of acetone and 0.5 parts by weight of maleic anhydride using a Henschel mixer, by granulating at 240 ° C. with a 40 mmφ extruder, a crystallinity of 15%, A maleic anhydride-grafted ethylene / 1-butene random copolymer having an MFR of 3 g / 10 min and a maleic anhydride graft amount of 0.35% by weight was obtained.

As the amorphous polyester (B-1) which becomes the domain layer, 90/10/85 / of isophthalic acid / terephthalic acid / ethylene glycol / 1,3-bis (2-hydroxyethoxy) benzene / trihydroxymethylpropane 15/0.
Copolymerization with a 3 mol composition was performed to obtain an amorphous polyester with IV = 0.85 dl / g.

The above resins A-1 and B-1 are used in the weight ratios shown in Table 1, and when the respective ratios are mixed, 1/1 of the total weight of A-1 and B-1
As a filler (D-1), talc (Cycloace P-3 average particle size 1.8 μ) manufactured by Nippon Talc was mixed in an amount of 100, and γ-glycidoxypropyltrimethoxy was used as a silane coupling agent (C-1). Silane A-1 and B-
1/100 of the total weight of 1 was mixed dropwise.

After granulating this with a 40 mmφ extruder, T-die film molding was performed to obtain a 70 μ film.

This film was sandwiched between two 0.8 mm-thick low carbon steel sheets that had been subjected to degreasing treatment with an alkaline detergent, and press-molding was performed at 190 ° C. for 10 minutes to obtain a damping steel sheet.

A 25 mm wide T-type peeling test was performed on the obtained damping steel sheet at a tensile speed of 100 mm / min. Further, a part of the steel sheets of both outer layers was cut, and a shearing test of the core resin with respect to an area of 20 mm width × 10 mm length was performed at a tensile speed of 10 mm / min. The vibration loss coefficient η was measured by the cantilever resonance point vibration damping method. The results are shown in Table 1.

Example 5 Resins A-1 and B-1 were prepared by the same means as in Example 1,
The modified polyolefin (E-1) consisting of low density polyethylene, methacrylic acid and butyl acrylate was added to the matrix layer and mixed in a weight ratio of A-1 / B-1 / E-1 = 33/67/13. At this time, C-1 and D-1 were added in the same manner as in Example 1, and a vibration-damping steel sheet was obtained by the same procedure below, and the evaluation results are shown in Table 1.

Example 6 The resin E-1 of Example 5 was treated with sodium ions to give an ionomer, and the results of evaluation as a substitute for the resin E-1 in the same manner as in Example 5 are shown in Table 1.

Example 7 As a result of adding the silane coupling agent C-1 in an amount of 1/200 in the same manner as in Example 2, the T peel strength was 20 kg / 20 mm,
The shear strength was 120 kg / cm ² .

Example 8 As a result of setting the amount of C-1 added to 1/25 in the same manner as in Example 7, the T peel strength was 25 kg / mm, the shear strength was 180 kg / cm ² , and
The film formation of the 70μ film was a little difficult.

Example 9 The amount of filler D-1 added was 1/20 in the same manner as in Example 2.
As a result of setting the amount to 0, some blocking was observed in the mixture at the time of granulation.

Example 10 The amount of filler D-1 added was 1/25 in the same manner as in Example 2.
As a result, the T peel strength is 12 kg / 25 mm and the shear degree is 130 kg / c.
It was unstable at m ² .

Comparative Example 1 Resin A-1 and silane coupling were carried out by the same means as in Example 1.
Exclude Agent C-1 and Filler D-1
Eastman Kodak Company Kodar PETG6763 only
Table 1 shows the evaluation results of.

Comparative Example 2 Table 1 shows the evaluation results of the resin layer B-1 of Example 1 used as the domain layer of Comparative Example 1.

Comparative Examples 3 to 6 By the same procedure as in Example 1, a film obtained by removing the silane coupling agent C-1 and the filler D-1 was obtained, and further a maleic anhydride-modified high-density polyethylene 15 .mu. Film for improving the adhesive strength. A two-layer, three-layer film
The vibration-damping steel plate was obtained by the same procedure as in Example 1, and the evaluation results are shown in Table 1.

Comparative Example 7 In the matrix layer of Example 2, resin A-1 and maleic anhydride-modified high-density polyethylene having a crystallinity of 60% were mixed at 7: 3.
Although the mixture was changed to a mixture having a weight ratio, the result of evaluation by the same method was a T peel strength as low as 2 kg / 25 mm, which was unsatisfactory.

Comparative Example 8 The ratio of the resins A-1 and B-1 was 20: 8 in the same manner as in Example 1.
The 0 weight ratio is 100 when the film is formed using the T-die.
It was difficult to obtain a thin film having a thickness of μ or less.

From these results, the characteristics as a damping steel plate required for automobile engine peripheral applications (oil pans, cylinder covers, etc.), that is, T peel strength 10 kg / 25 mm or more, core shear strength 100 kg / cm ² or more, and vibration loss Coefficient η is 80-1
High value in the range of 00 ° C (η is 0.1 or more in at least part)
It can be seen that the above three conditions are simultaneously achieved by the present invention.

An electron micrograph of the cross section of the core film obtained in Example 2 is shown in FIG. Here, it can be seen that the granular portion is polyester and forms a domain layer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a micrograph showing the particle structure of the resin composition for damping material of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 67/00 LPB // F16F 9/30 (C08K 13/02 3:00 5:54)

Claims (5)

[Claims] 1. A low crystalline polyolefin (A) modified with an unsaturated carboxylic acid, an amorphous polyester (B), a silane coupling agent (C) and an inorganic filler (D). A) is 30-60wt%, (B) is 40
˜70 wt%, 0.05 to 4 parts by weight of (C) and 0.5 to 4 parts by weight of (D) are added per 100 parts by weight of the total amount of (A) and (B). A resin composition for a vibration damping material, characterized in that (B) is a domain phase in a matrix phase. 2. The crystallinity of low crystalline polyolefin is 20%.
The resin composition for a vibration damping material according to claim 1, which is as follows. 3. The resin composition for a vibration damping material according to claim 1 or 2, wherein the unsaturated carboxylic acid is maleic acid, nadic acid or an acid anhydride thereof. 4. The dicarboxylic acid component of the amorphous polyester (B) comprises isophthalic acid at 15 to 100 mol%, terephthalic acid at the balance, and 5-90 mol% of the dihydroxy compound component at 1,3-.
The vibration damping according to any one of claims 1 to 3, wherein bis (2-hydroxyethoxy) benzene and / or 1,4 bis (2-hydroxyethoxy) benzene with the balance being ethylene glycol. Resin composition for wood. 5. The resin composition for vibration damping material according to claim 1, wherein the silane coupling agent (C) is γ-glycidoxypropyltrimethoxysilane. .