JPS6389553A - Non-crystalline polyester composition and use thereof - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent adhesion to metal, water- resistant adhesiveness and damping performance under high-temperature conditions and useful as a damping material, consisting of an unsaturated carboxylic acid-modified lowly crystalline polyolefin, a non-crystalline polyester and silane coupling agent. CONSTITUTION:100pts.wt. in total of 30-60wt% unsaturated carboxylic acid- modified lowly crystalline polyolefin (A) obtd. by grafting 0.3-0.6pts.wt. unsaturated carboxylic acid (e.g., maleic acid) onto 100pts.wt. lowly lowly crystalline polyolefin having a crystallinity index of not highter than 20% and 70-30wt% non-crystalline polyester (B) having an intrinsic viscosity of not lower than 0.6dl/g and a glass transition temp. of 40-100 deg.C wherein 15-100mol% of its dicarboxylic acid component is composed of isophthalic acid and the remainder thereof is terephthalic and 5-90mol% of its dihydroxy compd. component is composed of 1,3-bis(2-hydroxyethoxy)benzene and/or 1,4-bis(2-hydroxyethoxy) benzene and the remainder thereof is ethylene glycol, is blended with 0.05-4pts. wt. silane coupling agent (C) (e.g., r-flycidoxy propyltrimethoxysilane) The component A serves as a matrix layer and the component B serves as a domain layer.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a vibration damping material that has good adhesion to different materials such as metals, and more specifically, a damping material that has good water-resistant adhesion and is suitable for use in high-temperature regions. This invention relates to vibration damping materials with excellent vibration damping performance.

[Conventional technology]

Regarding compositions consisting of polyester and modified polyolefin, Japanese Patent Publication No. 59-28223 describes a composition in which polyester is a matrix phase and modified polyolefin is a domain phase, and Japanese Patent Publication No. 57-5405
No. 8 discloses that a modified polyolefin is used as a polyester.
A composition is described in which the composition is blended at a ratio of /10 to 4 times. Furthermore, JP-A-57-203546 describes a metal body coated with a resin composition of a polyolefin that may be modified and a polyester that may be amorphous.

Regarding a composition containing a silane coupling agent, JP-A-60-253536 discloses a vibration damping layer composed of a viscoelastic material as an intermediate layer which may contain a filler treated with a silane coupling agent. JP-A-55-31838 describes a sandwich steel plate having an intermediate layer made of a molten mixture of a polyolefin, a silane coupling agent, a filler, and a radical generator.

[Problems with conventional technology]

Among the above-mentioned conventional techniques, Japanese Patent Publication No. 59-28223 aims to improve the impact properties of polyester. Of course, only crystalline polyesters are disclosed. Moreover, there is no description of the formulation of the silane coupling agent, and there is no description or suggestion of adhesion with dissimilar materials such as metals or vibration damping performance. Special Publication No. 57-54058 also
The purpose is to improve impact properties, so all those disclosed as polyesters are crystalline. Moreover, as in the above publication, the combination of silane coupling agent,
There is also no suggestion about adhesion with different materials and vibration damping performance. JP-A-57-203546 does not have any suggestion regarding the combination of the silane coupling agent and the damping performance. JP-A-60-253536 does not mention amorphous modified low-crystalline polyolefin, and furthermore, the silane coupling agent is used to improve dispersibility when compounding the filler, and is not used alone. There is no suggestion of using it in JP-A-55-31838 also requires the presence of a filler, and as can be seen from its composition, the silane coupling agent is used to graft-modify the base polyolefin, and of course it is used for amorphous polyester and modified low-crystalline polyester. There is also no suggestion regarding polyolefins.

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

[Problem that the invention seeks to solve]

An object of the present invention is to provide an amorphous polyester composition that has good adhesion to different materials such as metals, that is, initial adhesion and water-resistant adhesion. Another object of the present invention is to provide an amorphous polyester composition that has excellent vibration damping performance, particularly in a high temperature range of 80 to 100°C. Further objects of the present invention will become apparent from the description of the specification below.

Means for Solving Problem C] That is, the present invention provides low crystalline polyolefin (A) modified with unsaturated carboxylic acids, amorphous polyester (B
) and a silane coupling agent (C), in which (A) is 30 to 60 (4) t%, (B)
is 40 to 70 wt% and the total amount of (A) and (B) is 10
0.05 to 4 parts by weight of (C) per 0 parts by weight, and (
The present invention relates to an amorphous polyester composition characterized in that A) is a matrix phase and (B) is a domain phase, and further relates to a vibration damping material made of the resin composition.

[For production]

The low-crystalline polyolefin that is the base of the modified low-crystalline polyolefin that is one component of the amorphous polyester composition of the present invention is a polyolefin with a degree of crystallinity of 20% or less, including ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-
Examples include homopolymers or mutual copolymers of α-olefins such as octene and 1-decene.

Examples of the unsaturated carboxylic acids used to modify the low-crystalline polyolefin include acrylic acid, methacrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and methyl. Tetrahydrophthalic acid, endocis-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid (nadic acid 0) methyl-endocys-bicyclo(
2,2,1) Unsaturated carboxylic acids such as hebdo-5-ene-2,3-dicarboxylic acid (methylnadic acid @), acid halides, amides, imides, acid anhydrides, and esters of the unsaturated carboxylic acids Specific examples include derivatives of unsaturated carboxylic acids such as maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and the like. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

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

Examples of the amorphous polyester (B) include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and hexamethylene glycol; alicyclic glycols such as cyclohexane dimetatool; Bisphenol, 1.3
-bis(2-hydroxyethoxy)benzene, 1.4-
An aromatic dihydroxy compound such as bis(hydroxyethoxy)benzene, or a dihydroxy compound unit selected from two or more of these, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, oxalic acid, Succinic acid, adipic acid, sebacic acid,
Amorphous resin among polyesters formed from aliphatic dicarboxylic acids such as undecadicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, or dicarboxylic acid units selected from two or more of these. And,
As long as it exhibits thermoplasticity, it may be modified with a small amount of a trivalent or higher polyhydroxy compound such as triol or tricarboxylic acid, or polycarboxylic acid. Specifically, these amorphous polyesters include dicarboxylic acid component 15
An amorphous isophthalate polymer consisting of a dicarboxylic acid component of ~100 mol%, preferably 50-100 mol% of isophthalic acid and the remainder of other dicarboxylic acid components such as terephthalic acid, and a dihydroxy compound component such as ethylene glycol. Examples include amorphous terephthalate copolymers consisting of a dicarboxylic acid component consisting of terephthalic acid and a dihydroxy compound component in which 15 to 50 mol% is cyclohexane dimetatool and the remainder is another dihydroxy compound component such as ethylene glycol. It will be done.

Among the amorphous isophthalate polymers, the remainder of the dicarboxylic acid component is 5 to 90 mol% of terephthalic acid and a dihydroxy compound, and more preferably 10 to 15 mol% is 1.
The same blend of isophthalate polymers consisting of 3-bis(2-hydroxyethoxy)benzene or 1,4-bis(2-hydroxyethoxy)benzene and 10 to 95 mol%, and even 75 to 90 mol% of ethylene glycol. It is preferable because it has a large vibration damping property at a temperature of 80 to 100°C.

The glass transition temperature of these amorphous polyesters (B) (
Tg) exists in various ranges, but is usually about 40 to 10
The temperature is 0°C, preferably 50-60°C.

Amorphous in the present invention refers to a resin that does not devitrify due to crystallization when left in an atmosphere at 190°C for 3 hours or more, and does not have a clear crystallization or crystal melting peak when measured by DSC. It is resin. Tg is a value determined from the transition point of latent heat during heating by DSC at a heating 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 inhibit the film formability of the composition, but it is usually 0-chloro/-/1z25°C.
In Le 1. V, is 0.6 dl/g or more, preferably 0
．． It is in the range of 8 to 0.9 a/g.

As a commercially available brand of amorphous polyester (B) as mentioned above, Eastman
There are Kodak products such as KODAR@PETG and PCTA.

The silane coupling agent (C) is used to improve the adhesion of the composition comprising the modified low-crystalline polyolefin (A) and the amorphous polyester (B), especially the initial adhesion of the composition with different materials such as metals during high-speed lamination. It is blended to improve water-resistant adhesion. In addition, by blending the silane coupling agent (C), the vibration loss coefficient η becomes larger at the same blending ratio of (A) and (B) compared to one without the silane coupling agent. , which also shows an unexpected effect of improving vibration damping performance.

Various known silane coupling agents can be used, but γ-glycidoxypropyltrimethoxysilane or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is preferred, with the former being especially preferred. is preferred. However, silane coupling agents other than these may be used, and specific examples of such silane coupling agents are given in "Crosslinking Agent Handbook" published by Taiseisha, Vol.
Examples are given on pages 58-561.

The composition of the present invention comprises the former (A), (B) and (C).
A blend of ingredients, where the ratio of each ingredient is (A) 3
0 to 601% preferably 40 to 50 wL% (B) is 40
~70-t%, preferably 50-60 t%, (C) is (
The sum of A) and (B) fi! 0.0 per 100 parts by weight
The amount is 5 to 4 parts by weight, preferably 1 to 2 parts by weight. moreover,
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 resins constituting the matrix phase and the domain phase are reversed to the above, long-term water-resistant adhesive durability cannot be expected due to the water absorbing properties of polyester, and thin film formation may be difficult. also poses a problem.

In addition, as the modified polyolefin, a modified low-crystalline polyolefin is used as described above, but if a modified high-crystalline polyolefin is used, silane coupling will occur in a blend system with an amorphous polyester. Even if adhesives are used together, sufficient adhesive strength cannot be achieved,
Even when adhesively laminated with dissimilar materials such as metals, internal resin cohesive failure is likely to occur due to low stress, and moldability is likely to be poor. In addition, if the proportion of (A) in the above blending ratio is too small, the composition of the matrix phase and domain phase will be reversed, resulting in a composition with poor adhesiveness and processability, and conversely, if it is too large, the vibration damping performance will deteriorate. descend. If the proportion of (C) is too small, there will be no improvement in water-resistant adhesion (and no improvement in vibration damping performance will be seen).In addition, if it is too large, it will become too hard, resulting in a decrease in vibration damping performance and poor workability. Go in the direction of becoming.

Note that 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), (B)
A method for simultaneously melt blending (C), (B) and (
There is a method of melt-blending C), then adding (A), and further melt-blending.

The composition of the present invention may also contain other resins to the extent that its properties are not significantly impaired. Examples of such resins include ethylene/(meth)acrylic acid copolymers, ethylene/(meth)acrylate copolymers, and ethylene/(meth)acrylic acid ester copolymers. Of course, it will be obvious to those skilled in the art that other known resins may be used.

Although the composition of the present invention is suitable for various uses, it can particularly be used as a vibration damping material, particularly as a high temperature vibration damping material, by taking advantage of its vibration distribution performance.

That is, the composition of the present invention has a temperature of 80°C or higher, particularly 80-1
It has a large loss coefficient η at temperatures of 00°C and is suitable for use as an allocating material for areas around the engine such as an oil pan. In this case, it is often used in the form of a composite laminate with metal plates.

Next, a method of using the damping material of the present invention as a damping material made of a composite laminate will be described. The composite laminate for vibration damping material has at least an outer layer made of metal, and at least one of the middle layers
The layer is an allocation material made of the above composition, and the metal layer may form not only the outer layer but also one of the intermediate layers.

As the structure of the composite laminate, the following structure can be exemplified.

(+) Metal/Composition (ii) Metal/Composition/Metal (iii) Metal/Composition/Metal/Composition (iv) Metal/
Composition/metal/composition/metal Among the composite laminates having these configurations, the three-layer composite laminate (ii) is particularly preferably used.

The structure of the composite laminate includes a plate-like body, a cylindrical body, a prismatic body,
It can be used as a shaped body of any other arbitrary structure.

Examples of metals constituting the composite laminate include iron, metal, copper, aluminum, stainless steel, brass, and porcelain. The thickness of the metal is arbitrary, but usually 0.1 to 2 mm, preferably 0.2 to 0.4 mm.
is within the range of Moreover, the thickness of the composition layer is also arbitrary, but
Usually 0.02-3mm, preferably 0.03-0.1
5mm range teal.

〔Effect of the invention〕

According to the present invention, it is possible to provide a damping material with excellent vibration damping performance, particularly in the low-temperature range, and also to provide a composition with excellent adhesion to different materials, that is, initial adhesion and water-resistant adhesion. .

〔Example〕

Hereinafter, the content of the present invention will be explained using preferred examples, but the present invention is not limited to these examples unless otherwise specified.

Examples 1 to 4 100 parts by weight of an ethylene/1-butene random copolymer with a crystallinity of 17% and an ethylene content of 90 mol% as the unsaturated carboxylic acid-modified low-crystalline polyolefin (A-1) to serve as the matrix layer. A mixed solution consisting of 0.015 parts by weight of acetone and 0.5 parts by weight of maleic anhydride was mixed dropwise using a Henschel mixer, and then granulated at 240'C with a 40 mmφ extruder to crystallize. degree 15
%, MFR of 3 g/10 m1n, and a maleic anhydride grafted ethylene/1-butene random copolymer having a maleic anhydride graft of 10.35% by weight.

In addition, as the amorphous polyester (B-1) serving as the domain layer, isophthalic fi/terephthalic acid/ethylene glycol/l and 3-bis(2-hydroxyethoxy)benzene/trihydroxymethylpropane are each used at 90/1.
0/85/15/ Perform copolymerization with a 0.3 molar composition, and
,■,=0.85d! /g amorphous polyester was obtained.

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

This was granulated using a 40 mmφ extruder and then subjected to T-die film molding to form a 70 μm film.

This film was subjected to alkaline detergent degreasing treatment.
Scissors between two m-thick low carbon steel plates, 190℃, 10
A damping steel plate was obtained by press forming for 1 minute.

A T-shaped peel test with a width of 25 mm was performed on the obtained damping steel plate at a tensile speed of 100 mm/min. In addition, a part of the steel plates of both outer layers was cut, and a shear test of the core resin was performed on an area of 20 mm width x 10 mm length at a tensile speed of 10 mm/m.
I went in. In addition, the vibration loss coefficient η was measured using the cantilever resonance point vibration damping method. These results are shown in Table 1.

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

Example 6 Resin D-2 of Example 5 was treated with sodium ions to form an ionomer and evaluated as a substitute for resin D-1 in the same manner as in Example 5. Table 1 shows the results.

Example 7 As a result of using the same method as in Example 2 and changing the amount of silane coupling agent C-1 to 1/200, the T peel strength was 20
kg/25mm, shear strength is 120 kg/
It was cat.

Example 8 As a result of using the same method as Example 7 and reducing the amount of C-1 added to 1/25, the T peel strength was 25 kg/25 mm and the shear strength was 180 kg/cd, making it somewhat difficult to form a 70 μ film. Met.

Comparative Example 1 Resin A-1 and silane coupling agent C-1 were removed by the same means as in Example 1, and the domain layer was made of Eastman Kodak Kodar@PET G 6763. The evaluation results are shown in Table 1. .

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

Comparative Examples 3 to 6 Following the same procedure as in Example 1, a film was obtained from which the silane coupling agent C-1 was removed, and a film was sandwiched between two 15μ films of maleic anhydride-modified high-density polyethylene to improve adhesive strength. A damping steel plate was obtained using the layered film in the same manner 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 with a crystallinity of 60% were mixed.
:3 weight ratio was used, but the evaluation result using the same method was that the T peel strength was as low as 2 kg/25 mm, which was poor.

Comparative Example 8 The ratio of resins A-1 and 8-1 was set to 20 using the same method as in Example 1.
: When the weight ratio was 80, it was difficult to obtain a thin film of 100 μm or less during film formation using a T-die.

These results show that the properties required as a vibration-damping steel plate for automotive engine peripheral applications (oil pans, cylinder covers, etc.) are as follows: T peel strength of 10 kg/25 mm or more, core shear strength of 100 kg/cm or more, and vibration. It can be seen that the present invention simultaneously achieves three conditions in which the loss coefficient η is a high value in the range of 80 to 100°C (at least in some cases η is 0.1 or more).

[Brief explanation of the drawing]

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

Claims (8)

[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), wherein (A) is 30 to 60wt%, (B) 40-70wt
% and per 100 parts by weight of the total amount of (A) and (B) (
An amorphous polyester composition characterized in that C) is 0.05 to 4 parts by weight, and (A) is a matrix phase and (B) is a domain phase. (2) The composition according to claim 1, wherein the low crystallinity polyolefin has a crystallinity of 20% or less. (3) Unsaturated carboxylic acids are maleic acid and najitsuk^■
Claim 1 which is an acid or an acid anhydride thereof
The composition according to item 1 or item 2. (4) 15 to 100 mol% of the dicarboxylic acid component of the amorphous polyester (B) is isophthalic acid, the remainder is terephthalic acid, and 5 to 90 mol% of the dihydroxy compound component is 1.3
Claim 1: -bis(2-hydroxyethoxy)benzene and/or 1,4-bis(2-hydroxyethoxy)benzene, with the remainder being ethylene glycol.
The composition according to any one of Items 1 to 3. (5) Claim 1, wherein the silane coupling agent (C) is γ-glycidoxypropyltrimethoxysilane.
The composition according to any one of Items 1 to 4. (6) (A) is 40-50wt%, (B) is 50-60wt%
6. The composition according to claim 1, wherein the amount of (C) is 1 to 2 parts by weight per 100 parts by weight of wt% and the total amount of (A) and (B). (7) Consists of a resin composition consisting of a low-crystalline polyolefin (A) modified with unsaturated carboxylic acids, an amorphous polyester (B), and a silane coupling agent (C), in which (A) weighs 30 to 60 wt. %, (B) is 40-70wt
% and per 100 parts by weight of the total amount of (A) and (B) (
A damping material characterized in that C) is 0.05 to 4 parts by weight, and (A) is a matrix phase and (B) is a domain phase. (8) The damping material according to claim 7, which is laminated with metal.