JPH073109A - Polyamide resin composition and laminate made by using the same - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in thermal adhesion characteristics and suitable for co-extrusion with a film grade nylon resin by blending a specified linear aliphatic nylon copolymer and a specified modified polyolefin resin. CONSTITUTION:The composition consists of 40-98wt.% linear aliphatic nylon copolymer having a melting point of 130 deg.C or lower and 2-60wt.% modified polyolefin resin obtained by grafting a polyolefin resin composed mainly of ethylene with an alpha,beta-unsaturated carboxylic acid or its derivative. The laminate should have a layer of this composition as an outermost layer at least on one side with at least one layer comprising other polyamide resin among other layers, and it may also have a polyolefin layer comprising, e.g. polypropylene or polyethylene. The composition can provide a nylon laminate film suitable for thermal adhesion to, e.g. a nonwoven fabric, such as a polyester nonwoven fabric, or a woven fabric.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyamide resin composition. More specifically, the present invention relates to a polyamide resin composition which has excellent thermal adhesiveness and is suitable as a resin material that can be coextruded with a nylon resin such as nylon 6 or nylon 6 / 6.6 copolymer.

[0002]

2. Description of the Related Art Nylon films such as nylon 6 or nylon 6 / 6.6 copolymers have excellent heat resistance, chemical resistance, weather resistance and tensile properties, and can be heat-bonded to woven fabrics and nonwoven fabrics. Although it is used, it is inferior in thermal adhesiveness by itself, and therefore, a linear aliphatic nylon having a melting point of 130 ° C. or less was laminated as an adhesive layer and heat-bonded to a woven fabric or a non-woven fabric. .

[0003]

The method for forming this adhesive layer includes, specifically, a dry lamination method and a coextrusion method, but a linear aliphatic nylon copolymer having a melting point of 130 ° C. or less is used. However, because of its low melt viscosity, coextrusion film molding with nylon resin for films such as nylon 6 or nylon 6 / 6.6 copolymer was difficult. Therefore, it has not yet been achieved to obtain a nylon laminate having excellent heat-adhesiveness by coextrusion molding, which has a simple process and is inexpensive.

That is, an object of the present invention is to provide a polyamide resin composition and a non-woven fabric which are excellent in thermal adhesiveness and suitable for coextrusion molding with nylon resin for film such as nylon 6 or nylon 6 / 6.6 copolymer. Another object of the present invention is to provide a polyamide resin laminate excellent in heat adhesion with.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, have a melting point of 130.
A composition obtained by blending a linear modified aliphatic nylon copolymer at a temperature of not more than 0 ° C with a specific modified polyolefin resin in a specific ratio,
The present invention has been found to meet such a purpose and has reached the present invention.

That is, the gist of the present invention is that (A) the melting point is 1
Linear aliphatic nylon copolymer 40 to 9 at 30 ° C or lower
Polyamide resin composition comprising 8% by weight and (B) 2 to 60% by weight of a modified polyolefin resin obtained by grafting an α, β-unsaturated carboxylic acid or a derivative thereof on a polyolefin resin having an ethylene component as a main constituent In a polyamide resin laminate using.

The present invention will be described in detail below. In the composition of the present invention, the nylon copolymer used as the component (A) has a melting point of 130 ° C. or lower, and specifically, lauryllactam, ω-12-aminocarboxylic acid or ω-11. -Aminocarboxylic acid-based 3
Examples include nylon copolymers of the original and above. Nylon monomers that can be copolymerized include nylon 6,66,6
Monomers such as 10,612 can be utilized.

As a concrete combination, nylon 6/6
6/12, Nylon 6/610/12, Nylon 6/6
6/610/12, nylon 6/66/11/12, etc. Examples of commercially available products include Griltex 1G (trade name) manufactured by Ems Japan. The polymerization ratio of these copolymers must be selected so that the melting point is 130 ° C or lower, preferably 80 to 130 ° C. This is because if the melting point exceeds 130 ° C., the thermal adhesiveness, which is the characteristic feature of the straight chain aliphatic nylon copolymer as the component (A), cannot be obtained. The polymerization ratio having such a melting point is not particularly limited, but it is preferable that the nylon 12 (lauryl lactam) component is 30 to 60% by weight.

The melting point referred to here is, for example, Per.
It shows the melting maximum peak temperature when measured at a temperature rising rate of 10 ° C./min with a differential calorimeter DSC-1B manufactured by Kin Elmer. The modified polyolefin resin as the component (B) of the present invention includes ethylene and α having 3 or more carbon atoms.
-Olefin copolymer (hereinafter referred to as "unmodified ethylene copolymer"), α, β-unsaturated carboxylic acid or a derivative thereof 0.0 to the unmodified ethylene copolymer
The one obtained by graft polymerization of 5 to 1.5% by weight is used.

The unmodified ethylene copolymer, which is the original family of the modified ethylene copolymer, uses, for example, a vanadium compound such as vanadium oxytrichloride and vanadium tetrachloride and an organoaluminum compound among Ziegler-Natta catalysts, Ethylene 50 mol% or more, preferably 80-9
An example is a copolymer of 5 mol% and 50 mol% or less, preferably 20 to 5 mol%, of an α-olefin having 3 or more carbon atoms.

As the α-olefin having 3 or more carbon atoms,
Propylene, butene-1, hexene-1, decene-1,
4-methylbutene-1, 4-methylpentene-1 and the like can be mentioned, but propylene or butene-1 is preferable. Suitable as such an unmodified ethylene copolymer is a series of resins sold by Mitsui Petrochemical Co., Ltd. under the trademark of Toughmer, for example, Tuffmer A40.
Toughmer A series (ethylene-butene-1 copolymer) such as 85, A4090, A20090, Tuffmer P0
Tuffmer P series (ethylene-propylene copolymer) such as 280, P0480, P0680, P0880 and the like can be mentioned.

The α, β-unsaturated carboxylic acid or its derivative (hereinafter simply referred to as unsaturated carboxylic acid) to be graft-polymerized on the above-mentioned unmodified ethylene copolymer includes acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid. Examples thereof include acids or anhydrides or esters of these acids. Of these, maleic anhydride is particularly preferable.

The amount of unsaturated carboxylic acid graft-polymerized on the unmodified ethylene copolymer is 0.05 to 1.5% by weight based on the unmodified ethylene copolymer. If this amount is too small, the surface compatibility of the molded product may be deteriorated due to poor compatibility with polyamide, which is not preferable. It is preferably in the range of 0.1 to 1% by weight. Graft polymerization is usually carried out by adding an unsaturated carboxylic acid to an unmodified ethylene copolymer according to a conventional method.
It is performed by melt-kneading at 50 to 300 ° C. In this graft polymerization, in order to efficiently cause the polymerization, α,
An organic peroxide such as α'-bis-t-butylperoxy-p-diisopropylbenzene may be used in an amount of about 0.001 to 0.05% by weight based on the unmodified ethylene copolymer.

The modified ethylene copolymer used in the present invention is
Crystallinity (Journal of Polymer Science, No. 1
XVII volume (1955), pages 17 to 26, measured by X-ray method) is 75% or less, preferably 1 to 35%, and melt index (ASTM
D 1238 57T at 190 ° C.).
It is preferably from 01 to 50, preferably from 0.1 to 20.

In order to prepare a modified ethylene copolymer having such a crystallinity and a melt index, an unmodified ethylene copolymer having a crystallinity and a melt index within the above ranges may be used. In the composition of the present invention, the blending amount of the nylon copolymer as the component (A) and the modified polyolefin resin as the component (B) is
40 to 98% by weight of the component (A) with respect to the total amount of the composition,
It is an essential requirement that the content of B component is preferably 50 to 90% by weight, and the content of B component is 2 to 60% by weight, preferably 10 to 50% by weight. When the blending amount of the nylon copolymer as the component (A) is less than 40% by weight, the heat adhesiveness, which is the characteristic feature of the component (A), is not exhibited. Also, the compounding amount is 98
When it exceeds the weight%, the performance is improved compared to the component (A) alone.
Specifically, the thickening effect is not recognized, and coextrusion with a nylon resin for films such as nylon 6 and nylon 6 / 6.6 becomes difficult. Therefore, in any case, a composition having desired properties cannot be obtained. The compounding is performed by a known method such as melt kneading.

The polyamide resin composition of the present invention has a sufficiently high melt viscosity, a good coextrusion moldability, and a low water absorption rate, so that stable mechanical properties can be maintained.
Therefore, a laminate having good thermal adhesiveness to a nonwoven fabric or the like can be obtained by coextrusion molding with another polyamide.
The coextrusion molding method may be any of conventionally known multilayer film molding methods such as inflation method, multi-many hold type T die molding, multilayer T die molding using a feed block, and multilayer T die molding using a stack plate. The bonding method may be inside or outside the die.

The polyamide resin to be coextruded with the composition of the present invention may be, for example, nylon 6, nylon 6 / 6.6 copolymer nylon 6.6, nylon 12, etc., as long as they are generally used for nylon films. Anything will do. The thickness constitution of each layer of the laminated film by this co-extrusion method is arbitrary, but it is preferable that the thickness of the polyamide resin composition layer is 70% or less based on the total thickness. This is because, as the thickness ratio of the polyamide resin composition layer increases, the gas barrier properties and the molding stability, which are characteristic features of the polyamide resin, may possibly decrease.

The laminate of the present invention has a layer composed of the polyamide resin composition of the present invention in at least one outermost layer, and the other at least one layer is another polyamide resin described above. In addition, it may have a polyolefin layer such as polypropylene or polyethylene.

[0019]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Reference Example: Production of modified polyolefin resin Ethylene-butene copolymer 10 having a melt index of 0.7 and a butene content of 20% by weight measured at 230 ° C.
0 parts by weight, 0.025 parts by weight of α, α'-bis-t-butylperoxy-p-diisopropylbenzene dissolved in a small amount of acetone, and 0.4 parts by weight of maleic anhydride were mixed with a Henschel mixer to obtain a mixture. The resin temperature is 230-240 ° C using a single screw extruder with a cylinder diameter of 40 mm.
Was melt-kneaded and pelletized. When a part of the obtained pellets was press-molded and maleic anhydride was quantified by infrared spectrum analysis, 0.32% of maleic anhydride was detected.

Examples 1 to 5 and Comparative Examples 1 to 2 Commercially available straight-chain aliphatic nylon copolymers as the component (A) [Griltex 1G (manufactured by EMS Japan), nylon 6 / 6.6 / 123] Original copolymer (Ny12 component 4
0% or more), melting point 105 ° C.] and the modified polyolefin resin obtained in the reference example as the component (B) in an amount ratio shown in Table 1, respectively, and using a twin-screw extruder in the same direction with a cylinder diameter of 30 mm, the resin temperature A polyamide resin composition was obtained by melt-kneading and pelletizing in the range of 130 to 180 ° C. The composition was molded by a multi-layer inflation molding method to obtain a laminated film having a layer structure shown in Table 1. That is, first, a film having the layer structure shown in Table 1 was formed by an inflation molding machine equipped with a three-layer, three-layer circular die having a lip diameter of 120 mm and a lip clearance of 1.0 mm.
It was confirmed whether or not the film could be formed.

Then, the surface of the composition of the present invention of the obtained three-layer film and the polyester non-woven fabric were hot-melt bonded at 130 ° C. under a pressing pressure of 1 kg. A test piece having a width of 15 mm was prepared from the laminated film after hot melt adhesion. This test piece is pulled at a pulling speed of 20 with an Instron type universal testing machine.
The 180 ° peel strength at 0 mm / min was measured. (2
3 ° C., 65% RHF) The results are shown in Table 1. In addition, in order to confirm the T-die multilayer film moldability, the lip width 450
mm, and a lip clearance of 1.0 mm were used to form a film having the same layer structure as shown in Table 1 with a three-kind three-layer T-die, and it was confirmed whether or not film forming was possible. The results are also shown in Table 1.

[0022]

[Table 1]

[0023]

As is clear from the results of Examples 1 to 5 and Comparative Examples 1 and 2, the composition of the present invention is excellent in thermal adhesion.
In addition, the coextrusion film moldability with a nylon resin for film such as nylon 6 and nylon 6 / 6.6 copolymer is good. Further, the polyamide resin composition of the present invention, because the water absorption is reduced, the deflection of the strength is reduced,
A laminate having stable physical properties can be provided. Therefore,
It is possible to provide a nylon laminated film suitable for thermal adhesion to a non-woven fabric such as a polyester non-woven fabric or a woven fabric.

Claims (2)

[Claims] 1. A polyolefin resin containing (A) 40 to 98% by weight of a linear aliphatic nylon copolymer having a melting point of 130 ° C. or less and (B) an ethylene component as a main constituent is α, β-unsaturated. A polyamide resin composition comprising 2 to 60% by weight of a modified polyolefin resin grafted with a carboxylic acid or a derivative thereof. 2. A polyamide resin laminate having a layer comprising the polyamide resin composition according to claim 1 as an outermost layer and at least another layer being another polyamide resin layer.