JPH0645736B2 - Amorphous polyester composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an amorphous polyester composition having good adhesion to different materials such as metals, and more particularly, to water-resistant adhesiveness at high temperature. The present invention relates to an amorphous polyester composition having excellent vibration damping performance in a range.

[Conventional technology]

Regarding the composition composed of polyester and modified polyolefin, JP 59-28223 discloses a composition in which polyester is a matrix phase, and modified polyolefin is a domain phase, and JP 57-54058 A discloses. A composition is described in which the modified polyolefin is blended in a ratio of 1/10 to 4 times the amount of polyester. Furthermore,
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.

Further, regarding a composition containing a silane coupling agent, Japanese Patent Application Laid-Open No. 60-253536 discloses that a viscoelastic substance, which may contain a filler treated with the silane coupling agent, is used as a vibration damping material. For example, JP-A-55-31838 describes a Sangerichi steel sheet 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 conventional techniques described above, Japanese Patent Publication No. 59-28223 discloses
It is intended to improve the 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, and naturally, 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 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 of compounding of a silane coupling agent, adhesion with different materials, and vibration damping performance. JP-A-57-2
The publication No. 03546 does not suggest the composition of the silane coupling agent and the vibration damping performance. In JP-A-60-253536, there is no description about the amorphous polyester-modified low-crystalline polyolefin, and moreover, the silane coupling agent is used for improving the dispersibility at the time of compounding the filler. There is no suggestion of using it alone.
JP-A-55-31838 also requires the presence of a filler, and as can be seen from the constitution, a silane coupling agent is used for graft-modifying a base polyolefin, and of course, an amorphous polyester or a modified low crystal is used. There is no suggestion about sex 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 an amorphous polyester composition having good adhesiveness to different materials such as metal, that is, initial adhesiveness and water resistant adhesiveness. Another object of the present invention is to provide an amorphous polyester composition excellent in vibration damping performance, particularly in a high temperature region of 80 to 100 ° C. 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 is a low-crystalline polyolefin modified with unsaturated carboxylic acids (A), a resin composition comprising an amorphous polyester (B) and a silane coupling agent (C), (A) is 30-60wt%, (B) 40-70wt% and (A) and (B)
(C) is 0.05 to 4 parts by weight per 100 parts by weight, and
(A) is a matrix phase and (B) is a domain phase, which is an amorphous polyester composition.

[Work]

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

The satiety used to modify the low crystalline polyolefin.
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, endocis-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
Specifically, maleenyl chloride, maleimide, maleic anhydride,
Citraconic anhydride, monomethyl maleate, maleic acid
Dimethyl and the like are exemplified. Among these, unsaturated di
Carboxylic acids or their anhydrides are preferred, especially
Leic acid, nadic acid or their anhydrides are preferred.
is there.

Modified low crystalline polyolefin (A) was obtained by grafting the above unsaturated carboxylic acids onto low crystalline polyolefin, usually 0.3 to 0.6 parts by weight per 100 parts by weight of 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, aliphatic glycols such as hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and bisphenol. 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.

Glass transition temperature (Tg) of these amorphous polyesters (B)
Are present in various ranges, but are usually about 40-100 ° C, preferably 50-60 ° C.

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.
IV 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 etc.
It

The silane coupling agent (C) is the adhesiveness of the composition comprising the modified low-crystalline polyolefin (A) and the amorphous polyester (B), especially the initial adhesiveness at the time of high-speed lamination with a dissimilar material such as a metal or It is added in order to improve water-resistant adhesion. In addition, by adding the silane coupling agent (C), compared to the one without the silane coupling agent, the vibration loss coefficient η in the same mixing ratio of (A) and (B) 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 the former is particularly preferable. 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 composition of the present invention is a blend of the former (A), (B) and (C) components, and the proportion of each component is (A) 30 to 60 wt%, preferably 40 to 50 wt% (B). 40-70 wt%, preferably 50-60 wt%,
(C) is 0.05 to 4 parts by weight, preferably 1 to 2 parts by weight, per 100 parts by weight of the total amount of (A) and (B). 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 when adhesively laminated with different kinds of materials such as metals, internal resin cohesive failure is likely to occur with low stress, and moldability tends to be poor. Further, in the above blending ratio, the composition of the matrix phase and the domain phase is too small or the composition of the domain phase is too small, resulting in a composition having poor adhesiveness and processability, and conversely if it is too large, the vibration damping performance decreases. To do. If the proportion of (C) is too small, the water-resistant adhesion 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.

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

To obtain the composition of the present invention, for example, a method of melt blending (A), (B) and (C) at the same time, melt blending (B) and (C), and then adding (A) and further melt blending. There are ways.

The composition of the present invention may be blended with other resins as long as the properties are not significantly impaired. 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 composition of the present invention is suitable for various uses, and it is possible to use it as a vibration damping agent, particularly as a vibration damping material for high temperature, by utilizing its vibration damping performance. That is, the composition of the present invention has a loss coefficient η at 80 ° C. or higher, particularly 80 to 100 ° C.
Since it is large, it is suitable for use as a vibration damping material for the engine peripheral part such as an oil pan. In this case, most are used in the form of a composite laminate with a metal plate.

Next, a method of using a part by weight of the vibration damping material as a vibration damping material composed of a composite laminate will be described. 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. 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 of (ii) having a three-layer structure 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. Moreover, the thickness of the composition layer is arbitrary, but is usually 0.02 to 3 m.
m, preferably in the range of 0.03 to 0.15 mm.

〔The invention's effect〕

According to the present invention, it is possible to provide an amorphous polyester composition having excellent vibration damping performance, particularly vibration damping performance in a high temperature range, and a composition having excellent adhesiveness with different materials, that is, initial adhesiveness and water resistant adhesiveness. 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, an ethylene / 1-butene random copolymer having a crystallinity of 17% and an ethylene content of 90 mol% is used.
To 100 parts by weight, 0.015 parts by weight of acetone and 0.
5 parts by weight of the mixture was added dropwise using a Henschel mixer and then granulated at 240 ° C with a 40 mmφ extruder to give a crystallinity of 15%, MFR 3 g / 10 min, and a maleic anhydride graft amount of 0.35. A weight% maleic anhydride grafted ethylene / 1-butene random copolymer was obtained.

As the amorphous polyester (B-1) that becomes the domain layer, isophthalic acid / terephthalic acid / ethylene glycol / 1,3-bis (2-hydroxyethoxy) benzene / trihydroxymethylpropane 90/10/85 / 15
A copolymer having a composition of 0.3 mol / 0.3 was obtained to obtain an amorphous polyester having IV = 0.85 dl / g.

The above resins A-1 and B-1 were mixed in the weight ratio shown in Table 1. At the time of each mixing, γ-glycidoxypropyltrimethoxysilane was added as A-1 and B as the silane coupling agent (C-1).
-1 was added dropwise by 1/100 of the total weight.

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 peel test was performed on the obtained damping steel sheet at a tensile speed of 100 mm. Further, a part of the steel plates of both outer layers was cut, and a shear test of the core material resin against an area of 20 mm width × 10 mm length was performed at a tensile speed of 10 mm / min. In addition, 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 in the same manner as in Example 1, and modified polyolefin (D-1) consisting of low-density polyethylene, methacrylic acid and butyl acrylate was added to the matrix layer, and A- They were mixed in a weight ratio of 1 / B-1 / D-1 = 33/67/13. At this time, C-1 was added in the same manner as in Example 1, and a vibration-damping steel plate was obtained by the same procedure below, and the evaluation results are shown in Table 1.

Example 6 The resin D-2 of Example 5 was treated with sodium ions to give an ionomer, and the results of evaluation as a substitute for the resin D-1 in the same manner as in Example 5 are shown in Table 1.

Example 7 As a result of setting the addition amount of the silane coupling agent C-1 to 1/200 in the same manner as in Example 2, the T peel strength was 20 kg / 25 m.
The m and shear strength were 120 kg / cm ² .

Example 8 As a result of using the same method as in Example 7 and setting the addition amount of C-1 to 1/25, the T peel strength was 25 kg / 25 mm, the shear strength was 180 kg / cm ² , and it was somewhat difficult to form a 70 μ film. It was.

Comparative Example 1 Resin A-1 and silane coupling agent C were prepared in the same manner as in Example 1.
-1 removed and domain layer Eastman Kodak Koda
r Table 1 shows the evaluation results of only PET G 6763.
You

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 In the same procedure as in Example 1, a film obtained by removing the silane coupling agent C-1 was obtained, and two 15 µ films of maleic anhydride-modified high-density polyester were used to further improve the adhesive strength. 3 Table 1 shows the evaluation results obtained by obtaining a vibration-damping steel sheet in the same procedure as in Example 1 using a layered film.

Comparative Example 7 Resin A-1 and crystallinity 6 in Example 2 and the matrix layer
0: 3% maleic anhydride modified high density polyester 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 When the ratio of the resins A-1 and B-1 was set to 20:80 by the same method as in Example 1, it was difficult to obtain a thin film having a thickness of 100 μ or less when forming a film using a T die. Atsuta

From these results, the durability as a damping steel plate required for automobile engine peripheral applications (oil pan, cinder cover, etc.), that is, T peel strength of 10 kg / 25 mm or more, and core material shear strength of 100 kg / cm ² or more, and vibration Loss factor η is 80 to 10
It can be seen that the present invention simultaneously achieves three conditions of high values (η is 0.1 or more in at least a part) in the range of 0 ° C.

[Brief description of drawings]

FIG. 1 is a micrograph showing the particle structure of the resin composition of the present invention.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 67/02 LPB 8933-4J // B32B 15/08 103 7148-4F 104 7148-4F

Claims (6)

[Claims] 1. A resin composition comprising a low crystalline polyolefin (A) modified with an unsaturated carboxylic acid, an amorphous polyester (B) and a silane coupling agent (C), which comprises (A)
Is 30 to 60 wt%, (B) is 40 to 70 wt% and the total amount of (A) and (B) is 1
An amorphous polyester composition, wherein (C) is 0.05 to 4 parts by weight, and (A) is a matrix phase and (B) is a domain phase, per 00 parts by weight. 2. The crystallinity of the low crystalline polyolefin is 20%.
The composition of claim 1 wherein: 3. The unsaturated carboxylic acids are maleic acid and nadiz.
Ku Claims which are acids or their acid anhydrides
The composition according to item 1 or 2. 4. The dicarboxylic acid component of the amorphous polyester (B) comprises 15 to 100 mol% of isophthalic acid, the balance terephthalic acid, and the dihydroxy compound component of 5 to 90 mol% of 1,3-bis (2-hydroxy). Ethoxy) benzene and / or
The composition according to any one of claims 1 to 3, wherein 1,4-bis (2-hydroxyethoxy) benzene and the balance ethylene glycol. 5. The composition according to any one of claims 1 to 4, wherein the silane coupling agent (C) is γ-glycidoxypropyltrimethoxysilane. 6. (A) 40 to 50 wt%, (B) 50 to 60 wt% and
The composition according to any one of claims 1 to 5, wherein (C) is 1 to 2 parts by weight per 100 parts by weight of the total amount of (A) and (B).