JPS6274641A - Laminated structure containing polyamide elastomer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The invention relates to a laminated structure having excellent vibration damping properties and adhesive properties.

<Prior Art> There is an increasing demand for vibration damping metal plates for use in reducing the weight of metal materials for automobiles and for noise prevention purposes. This type of metal plate 10 has been studied in the past, and various types have been proposed in which metal layers are bonded and laminated on both sides of a polymer intermediate layer.

For example, those using polyvinyl acetate lv type resin (Japanese Patent Publication No. 45-34703), those using nylon 12 type polyamide elastomer resin (Japanese Patent Publication No. 57-93)
Publication No. 139].

<Problems with Prior Art> Although the above-mentioned laminate has excellent vibration damping properties, there is a problem in that the temperature range in which it can be used is narrow, and the vibration damping performance deteriorates at temperatures outside this range.

The present invention has been made to overcome the above-mentioned drawbacks and to provide a polyamide elastomer-containing laminate structure with excellent adhesiveness and vibration damping performance over a wide range of temperatures.

Means for Solving Problems> The above objects of the present invention are as follows: (1) an aliphatic diamine having 6 to 20 carbon atoms; B) a substantially equimolar amount of an aliphatic diamine having 6 to 15 carbon atoms; Aliphatic dicarboxylic acid, (O number average molecular weight 300-6000
, poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine, and [DJ] a polyether ester amide polymer and/or a polyether amide polymer derived from a dicarboxylic acid having 4 to 20 carbon atoms. It has been found that this can be achieved by forming a polyamide elastomer-containing laminate structure by adhering and laminating metal layers on both sides of the intermediate layer.

The configuration, embodiments, and effects of the present invention will be described in detail below.

In the present invention, the aliphatic diamine having 6 to 20 carbon atoms, which is the A3 component, includes hexamethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, nonamethylene diamine, dodecamethylene diamine, hexadecamethylene diamine. Examples include.

Examples of the aliphatic dicarboxylic acid having 6 to 15 carbon atoms, which is component (8) in the present invention, include adipic acid, pimelic acid, superric acid, azelaic acid, cepacic acid, onedecanedioic acid, dodecanedioic acid, and brassylic acid. .

The above-mentioned prisoner component and (Bl component) are used in a substantially isoelectric state, so they should be prepared in the form of salt in advance.

Alternatively, both may be provided in a substantially equimolar mixture during the polymerization step. In particular, in the case of a reaction system that does not cause phenomena such as sublimation or distillation out of the system under the polymerization reaction conditions of diamines or dicarboxylic acids, it is not necessary to use the reaction as a salt in advance; Using it gives good results.

Examples of polyamide units derived from the above components (2) and Q3) include nylon 6.6, nylon 6.9, nylon 6.10. Nylon 6/12, nylon 8/6,
Nylon 8/10% Nylon 10/6, Nylon 10-
10. Nylon 11/6, nylon ll/10% nylon 11/12, nylon 12/6, nylon 12 bow 0,
Nylon 12.12 or the like is preferably selected.

The m of the nylon m-n used in this way.

The reason why n is limited to the above range E is mainly due to the relationship between the physical and chemical properties of the polymer and the polymerization characteristics.

If rr) + n is too small, the compatibility with component (i) in the present invention will be low, and a coarse phase-separated structure will be formed, making it impossible to obtain a homogeneous polymer. On the other hand, if m + n is too large, the melting point of nylon m - n will be low and the physical properties at high temperatures will not be sufficient.

Among them, a preferable polyamide unit is nylon 6.1O
, nylon 6/12, t-iron 11/6, and nylon 12/6. Furthermore, depending on the purpose and application, these amide-forming components can be used together, and other amide-forming components can also be copolymerized for purposes such as controlling the melting point of polyether ester amide. It is acceptable from a small amount range.

The number average molecular weight of component C) in the present invention is 300-300
6000 poly(alkylene oxide) glycols include polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol, poly(tetramethylene oxide fuglycol, poly(hexamethylene oxide) glycol, ethylene oxide and propylene oxide) Examples include block or random copolymers of ethylene oxide and tetrahydrofuran, and block or random copolymers of ethylene oxide and tetrahydrofuran.

The number average molecular weight of this poly(alkylene oxide) glycol can be used in the range of 300 to 6,000, but in reality, it is preferable to use a number within this range that does not cause coarse phase separation during polymerization and has good low-temperature properties and mechanical properties. An excellent molecular weight region may be selected and used. This optimum molecular weight range varies depending on the type of poly(alkylene oxide) glycol.

For example, in the case of polyethylene glyco-p, the molecular weight region is 3.
00-6000. In particular, it is preferably 1000 to 4000, and in the case of poly(propylene oxide glycol), the molecular weight range is 300 to 5000.
00 is preferable, and furthermore, in the case of poly(tetramethylene oxytone glyco-μ), the molecular weight range is 500 to 30.
00. Particularly preferred is 500 to 2,500.

In addition, the number average molecular weight of component C) in the present invention is 3.
00 to 6000 poly(alkylene oxide) diamine is a compound in which the hydrogen of the hydroxyl group (-OH) at both ends of the above-mentioned poly(7〃quinoxide) glycol compound is replaced with an aminoalkyl group (-RNH2). can be given. Note that the above R means a fullkylene group having 2 or more carbon atoms.

Among component C), poly(tetramethylene oxytone glycol) is preferably used because of its excellent physical properties as a polyamide elastomer, such as heat resistance, water resistance, mechanical strength, and elastic recovery.

4 or more carbon atoms used as component 1)) in the present invention
Examples of the dicarboxylic acids of No. 20 include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl A/-4,4'-dicarboxylic acid, and diphenoxyethane dicarboxylic acid. , aromatic dicarboxylic acids such as sodium 5-sulfoisophthalate + 1,4-cyclohexanedicarboxylic acid, 1°2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'
Mention may be made of alicyclic dicarboxylic acids I such as -dicarboxylic acids and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sepacic acid, dodecanedioic acid (decanedicarboxylic acid). Among them, terephthalic acid, Isophthalic acid % 1. Dicarboxylic acids such as 4-cyclohexane dicarboxylic acid, adipic acid, sepacic acid, and dodecadiic acid are preferably used from the viewpoint of the color tone and physical properties of the polyamide elastomer obtained.

The polyether ester amide polymer and/or polyether amide polymer formed by copolymerizing these components is
The amount of copolymerization of polyether ester units and polyether amide units derived from poly(alkylene oxytone glycol and/or poly(alkylene oxytone diamine) and dicarboxylic acid is 5 to 95% by weight.

The content should preferably be 20 to 90% by weight.

If the copolymerization amount is less than 5% by weight, vibration damping properties will be lost, and if it exceeds 9'% by weight, heat resistance and strength will not be sufficient.

The polymerization method for producing the polyether ester amide polymer from the above components is not particularly limited, and any conventional method may be used. For example, after adjusting the nylon salt from component (■) and component (B+).

(D) A method of reacting with component to produce a polyamide prepolymer having carboxylate salts at both ends, and reacting this prepolymer with poly(alkylene oxide) glycol under vacuum;
Alternatively, the nylon salt, each component (C) # and D) are charged into a reaction tank and heated to react at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then , there is a method of proceeding with polymerization under normal pressure or reduced pressure. Alternatively, there is a method in which the components of the nylon salt, C1 and D) are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum.This method has the advantage that the resulting polymer is less colored. preferred.

Alternatively, components (2) and B) may be directly subjected to the reaction without preparing a nylon salt from components (2) and (B) in advance.

The method for polymerizing this polyether ester amide is as follows:
Since this is a polyester type vacuum polymerization method, some sublimable components such as adipic acid are distilled off outside the reaction system during polymerization. For this reason, it is preferable to add a large amount of the above-mentioned phase increasing component in advance and polymerize it so as not to cause a shift in the molar balance between poly(alkylene oxide) glycol and adipic acid.

The following polymers and/or compounds can be blended with the polyether ester amide and polyether amide of the present invention.

Namely, polyamide elastomers, polyester elastomers, thermoplastic polyurethanes, polystyrene elastomers, 1°2-polybutadiene, polyolefin elastomers, polyepoxides, ethylene vinyl acetate copolymers (EVA), ethylene globylene rubber ( EPM%EPDM), ionomer resins are ethylene copolymers such as chlorinated polyethylene and chlorosulfonated polyethylene.

The polyether ester amide and polyether amide of the present invention contain antioxidants, thermal decomposition stabilizers, stabilizers such as light stabilizers, colorants, flame retardants, and reinforcing agents at any time during or after polymerization and before molding. , fillers, various molding aids, plasticizers, and other additives may be optionally blended and used.

The polyamide elastomer-containing laminate structure of the present invention is obtained by adhering metal layers to both sides of the intermediate layer made of the above polyether ester amide and polyether amide. The thickness of the polyamide elastomer film forming the intermediate layer is preferably 10 μm to 1 m. The method of adhering the polyamide elastomer and metal is not particularly limited.

For example, there is a method in which a polyamide elastomer film is extruded to form a molten film on a metal plate and then bonded as is, a method in which a polyamide elastomer film is formed and then heated and remelted to bond it to a metal plate, or a method in which a film and a metal plate are bonded together. Examples include a method of adhering using a known adhesive. Further, the type of metal plate is not particularly limited. Examples include steel plates, copper plates, brass plates, aluminum plates, etc., and the two metal plates may be of the same type or of different types.

<Examples> Unless otherwise specified in the examples, parts mean parts by weight.

Reference Example Polymerization run decafe of polymer (I), CH1. 16.8 parts of v7 diamine-adipate, 1λ5 parts of terephthalic acid, and 75.2 parts of poly(tetramethylene oxide) glyco-/l/ having a number average molecular weight of 1000 were mixed into "1 Iganox" 1109
80.5 parts (antioxidant) and 0.05 part of antimony dioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, purged with nitrogen, heated and stirred at 265°C for 1 hour to form a homogeneous transparent solution. , according to the decompression program 1
The polymerization conditions were brought to below 1 mHg in hours. When the reaction was carried out under these conditions for 465 hours, a viscous, colorless and transparent molten polymer was obtained, and this polymer was discharged into water as a gut to form chips. The obtained polyether ester amide (I) was dissolved in orthochlorophenol at 25
The relative viscosity (ηr) measured at ℃ and 0.5 part concentration is 2.0.
It is 6.

The crystal melting point by DSC was 184°C.

28.0 parts of polymerized undecamethylenediamine-adipate of polymer CI[),
Same as polymer CI) from 13.4 parts of terephthalic acid, poly(tetramethylene oxide) glyco-/L/64.5 parts %l Irganox 1110980.5 parts with a number average molecular weight of 800, and 0.05 parts of antimony dioxide The relative viscosity was 2.01. A polyether ester amide (n) having a melting point of 198°C was obtained.

Polymerized undecamethylenediamine-adipate of polymer (III) 44, 9. parts, 118 parts of adipic acid, poly(
Tetramethylene oxide) glyco-/L15L 3 parts,''
Irganox" 10980.5 parts and antimony trioxide 0.05 parts were polymerized under the same conditions as Polymer (I) to obtain a polyether ester amide Cm) having a relative viscosity of L93 and a melting point of 213°C.

22.6 parts of polymerized hexamethylenediamine-sepacic acid salt of polymer (IV), 19.8 parts of sepacic acid, 63.7 parts of poly(tetramethylene oxytone glycol having a number average molecular weight of 650), 980.5 parts of 1irganoxll O , and 0.05 part of antimony trioxide under the same conditions as Polymer (1) to obtain polyether ester amide (IV) having a relative viscosity of 198.8 and 171°C.

213 parts of polymerized hexamethylene diamine dodecanedioate, 18.5 parts of dodecanedioic acid, and poly(V) having a number average molecular weight of 800.
tetramethylene oxide) glyco-/L/64.4 parts,
Polyether ester amide (V) having a relative viscosity of 2.02 and a melting point of 169° C. was obtained by polymerizing 11 Irganox I + 10980.5 parts and 0.0.5 parts of antimony trioxide under the same conditions as polymer (I). .

The following polymers were used in comparative examples.

Polymer (Vl) 60.0 parts of laurolactam, poly(tetramethylene oxide) glyco/I/33 having a number average molecular weight of 1000.
5 parts and 7.7 parts of dodecanedioic acid with a relative viscosity of 2.05.

Polymer (■) A copolymer derived from vinyl acetate/l/64 parts, 18 parts of ethylene, and 118 parts of n-butylacrylic V-.

Examples 1 to 5 Comparative Example 1.2 Thickness of 0.12 by hot pressing from the polymer shown in the table
A film of m was prepared and thermally bonded between two steel plates of %150XloOxLQsw at a pressure of 2kg/12. The T peel strength of these laminated structures was determined based on JIS-6854. Also, the laminated structure is 200x
The sample was cut into a size of 1Um, and the temperature dependence of the loss coefficient was measured at a frequency of 300 Hz using a cantilever beam vibrating reed method. These results are also shown in the table.

As seen in the examples, the laminated structure of the present invention has high T-peel strength and excellent adhesion, exhibits a loss coefficient of O,1 or more over a wide temperature range, and exhibits poor vibration damping properties. I understand that.

<Effects of the Invention> The present invention has excellent vibration damping properties in a wide temperature range from low to high temperatures by using polyether ester amide and/or polyether amide having a specific material as an intermediate layer and bonding metal layers to both sides. It still has high adhesive strength and excellent workability.

Claims (1)

Scope of Claims: (A) an aliphatic diamine having 6 to 20 carbon atoms; (B) an aliphatic dicarboxylic acid having 6 to 15 carbon atoms in a substantially equimolar amount to the aliphatic diamine; (C) Poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine having a number average molecular weight of 300 to 6,000, and (D) a polyether ester amide polymer and/or derived from a dicarboxylic acid having 4 to 20 carbon atoms. Polyetheramide polymer is used as an intermediate layer,
A polyamide elastomer-containing laminate structure formed by adhering and laminating metal layers on both sides of the intermediate layer.