JPS6274644A - Laminated structure consisting of 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 Application Field> 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 lightweight automotive metal materials and noise prevention applications. This type of metal plate has been studied in the past, and a number of proposals have been made in which metal layers are bonded to both surfaces of an intermediate layer of a polymer material.

For example, those using polyvinyl acetate resin (Japanese Patent Publication No. 45-34703) and those using nylon 12-based polyamide elastomer resin combined with aliphatic dicarboxylic acid (Japanese Patent Publication No. 57-93139). can give.

Problems with the Prior Art> Although the above-mentioned M layer body has excellent M excitation damping properties, there is a problem in that the usable temperature range 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 single-channel body made of polyamide elastomer with excellent adhesiveness and vibration damping performance over a wide range of temperatures.

Means for Solving the Problems> The above objects of the present invention are: (1) an aminocarbonate and/or a lactam having 12 carbon atoms; (c) a poly(alkylene oxide) glycol having a number average molecular weight of 300 to 6000; A polyether ester amide polymer and/or a polyether amide polymer derived from a poly(alkylene oxide) diamine and an aromatic dicarboxylic acid having 8 to 20 carbon atoms is used as an intermediate layer, and on both sides of the intermediate layer. It has been found that this can be achieved by bonding and laminating metal layers to form a laminated structure made of polyamide elastomer.

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

The aminocarboxylic acid having 12 carbon atoms and/or 2cutam, which is the component (c) in the present invention, includes 12-
Examples include aminododecanoic acid and 2uro2cutam.

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

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 poly(alkylene oxide) glycol within this range to avoid coarse phase separation during polymerization and to have excellent low-temperature properties and mechanical properties. It is sufficient to select and use a molecular weight range.

This optimal molecular weight region is based on poly(alkylene oxide)
Depends on the type of glycol. For example, in the case of polyethylene glycol, the molecular weight range is preferably 300 to 6000, particularly 1000 to 4000, and in the case of poly(propylene oxide) glycol, the molecular weight range i [3
00 to 5000, particularly preferably 500 to 3000, and in the case of poly(tetramethylene oxide) glycol, the molecular weight range is 500 to 3000, particularly 500 to 3000.
2500 is preferred.

In addition, among the components (iii) in the present invention, the poly(alkylene oxide) diamine having a number average molecular weight of 300 to 6,000 is the hydroxyl group (-0) 1) at both ends of the above-mentioned poly(alkylene oxide) glycol compound. Examples include compounds in which the hydrogen of is substituted with an aminoalkyl group (-RNf(z)).The above R means an alkyref group having carbon a2 or more.

Among the above components, poly(tetramethylene oxide) glycol is preferably used because of its excellent physical properties as a polyamide elastomer, such as heat resistance, water resistance, +4 mechanical strength, and elastic recovery.

8 to 20 carbon atoms used as the Ω component in the present invention
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5- Examples include sodium sulfoisophthalate. Among them, terephthalic acid and isophthalic acid are preferably used from the viewpoint of polymerization reactivity and pseudophysical properties of the polyamide elastomer.

The polyether ester amide polymer and/or polyether amide polymer formed by copolymerizing these components is
The amount of copolymerization of polyetherester units and polyetheramide units derived from poly(alkylene oxide) glycol and/or poly(alkylene oxide) diamine and dicarboxylic acid is 5 to 95: jif
it%, preferably 72 to 95% by weight.

If the amount of "copolymerization" is less than 5% by N, vibration damping properties will be lost, and if it exceeds 95% by N, heat resistance and strength will not be sufficient.

The polymerization method for producing the polyether ester amide polymer from the above components is not limited in time and may be carried out using conventional methods. For example, a method may be used in which the above component (I) and (Q component) are reacted to produce a polyamide prepolymer having carboxylic acid groups at both ends, and this prepolymer is reacted with poly(alkylene oxide) glycol under vacuum; Components c), (c), and 0 are charged into a reaction tank and reacted by heating at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, followed by normal pressure or reduced pressure. There is also a method of proceeding the polymerization under high vacuum.Also, there is a method of simultaneously charging each of the components (1), (2), and (Q), melt polymerizing them, and then proceeding with the polymerization all at once under a high vacuum. , is preferable in that the resulting polymer is less colored.

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

i.e. polyamide elastomers with different copolymer compositions,
Polyester elastomer, thermoplastic polyurethane, polystyrene elastomer, 1゜2-polybutadiene, polyolefin elastomer, polyepoxide, ethylene vinyl acetate Jlt base (EVA), ethylene propylene rubber (EP+vf1EP DM), ionomer resin, chlorinated polyethylene , ethylene-based copolymers such as chlorosulfonated polyethylene.

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

The laminated structure made of the polyamide elastomer of the present invention is obtained by adhering metal layers to both sides of the intermediate layer made of the above-mentioned 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 are two methods: extrusion molding a polyamide elastomer to form a molten film on a metal plate and directly adhering it; a method in which a polyamide elastomer film is molded and then heated and remelted to adhere it to a metal plate; Examples include a method of adhering using a known adhesive. Further, iB of the 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 Polymer (Polymerization of In 19 parts of 12-aminododecanoic acid, 7 parts of terephthalate)
0 parts, and 845 parts of poly(tetramethylene oxide) glycol with a number average molecular weight M of 200 L+ were charged into a reaction vessel equipped with a stirring blade and nitrogen gas. After purging and heating and stirring at 260°C for 1 hour to obtain a homogeneous transparent solution, 15 parts of antimony dioxide catalyst α0, 0.015 parts of monobutyl monohydroxytin oxide catalyst, phosphorus aO
,005 parts (coloring inhibitor) were added, and the polymerization conditions were brought to below 1 flf (f) in 1 hour according to the vacuum program. When the reaction was carried out under these conditions for 3.5 hours, a viscous colorless and transparent molten polymer was formed. When this polymer was discharged into water as a gut, it crystallized and turned white.The obtained polyether ester amide (1) had a relative viscosity (ηr) measured in orthochlorophenol at 25°C at a concentration of 0.5%. was 2.11, and the crystal melting point by DSC was 109°C.

Polymerization of polymer (1) 12-aminododecane d 27.3 parts, terephthal 48,
1 part, 68.6 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1400, Irganox”
1098 0.5 part, antimony dioxide 0.015 part, motuptil monohydroxytin oxide 0.015 part,
9,710.005 parts of the mixture were prepared under the same conditions as in the polymer to obtain IJ ether ester amide with a relative viscosity of 2t9g and a melting point of 137°C.

Polymerization of Polymer I 49.1 parts of 2-aminododecane a, terephthal ag,
parts, 48.7 parts of poly(tetramethylene oxide) glycol with a number average molecular point of 1000, "Irganox"
1098 0.5 parts, antimony trioxide 0.015
Polyether ester amide (conversion) having a relative viscosity of L95 and a melting point of 153° C. was obtained by polymerizing under the same conditions as Polymer (1) from 0.015 parts of motuputyl monohydroxytin oxide and 0.005 parts of phosphoric acid. Ta.

Polymerization of Polymer GYI 16.4 parts of 2-aminododecane, 7.
7 parts, 79.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1700, “Irganox”
0.5 part of 1098, 0.015 part of antimony trioxide, 0.015 part of motuptil monohydroxytin oxide. U l 5
Polymerization was carried out using 1 part and 005 parts of phosphorus fiO under the same conditions as in the polymer to obtain polyetheresteramide GV) having a relative viscosity of L94 and a melting point of 122°C.

The following polymers were used in comparative examples.

Polymer (V) 60.0 parts of laurolactam, 33.5 parts of poly(tetramethylene oxide) glycol with a number average molecular point of 1000
and 7.7 parts of dodecane diυ, with a relative viscosity of 2.05.

Polymer (b) A copolymer derived from 64 parts of vinyl acetate, 18 parts of ethylene, and 18 parts of n-butyl acrylate.

Examples 1 to 4, Comparative Examples 1 and 2 Thickness 0.12 by hot pressing from the T polymer shown in the table
Create a film of the fin, 150X 100XLOIff
2 was thermally bonded between two steel plates with a pressure of 9/d.

The T peel strength of these laminated structures was determined based on JIS-6854. Also, the laminated structure is 200X
The sample was cut to a size of 10 fi, and the temperature dependence of the loss coefficient was measured at a frequency of 300 Hz using a cantilever type 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@ separation strength and excellent adhesion, exhibits a loss coefficient of 0.1 or more over a wide temperature range, and has excellent vibration damping properties. I understand that.

<Effects of the Invention> The present invention uses polyether ester amide and/or polyether amide having a specific structure as an intermediate layer and adheres metal layers to both sides, thereby improving vibration damping properties over a wide temperature range from low to high temperatures. It is. In addition, the adhesive strength is high and the processability is affected.

Patent application Daitoshi Co., Ltd.

Claims (1)

Scope of Claims: (A) an aminocarboxylic acid and/or a lactam having 12 carbon atoms; (B) a poly(alkylene oxide) glycol and/or a poly(alkylene oxide) diamine having a number average molecular weight of 300 to 6,000; and (C) carbon number 8-2
A laminated structure made of a polyamide elastomer, which has a polyether ester amide polymer and/or a polyether amide polymer derived from aromatic dicarboxylic acid of 0 as an intermediate layer, and metal layers bonded and laminated on both sides of the intermediate layer. .