JPH0368640A - Adhesive resin composition - 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 Technical Field of the Invention The present invention relates to an adhesive resin composition that provides excellent adhesion between a metal and a thermoplastic resin. It relates to an adhesive resin composition suitable for bonding.

Technical background of the invention The properties required for cable shielding materials have become more sophisticated, and there are now aspects that cannot be covered by a single material. For this reason, a laminated sheath cable was developed in which a shielding layer made of metal tape was provided on the outside of the cable core, and a resin sheath was provided on the outside of the shielding layer.

This laminate cable has been widely used in recent years because it has excellent properties such as mechanical properties, corrosion resistance, and moisture resistance.

In this laminated cable, the metal tape used for the shielding layer is made of aluminum, copper, etc., and the sheath resin is mainly made of low-density polyethylene, but it is difficult to bond the two together. Therefore, a fusion resin is placed between them to bond them together.

Conventionally, three components have been used as the fusion resin: ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as EVA), styrene polymer (hereinafter sometimes referred to as PS), and maleic anhydride graft-modified polyethylene. Good adhesion between the metal and resin sheath layers was obtained.

In the production of laminated metal tapes, the following methods are generally used: an extrusion lamination method of metal and a sheath resin, or a method of laminating each film layer of a metal layer, a fusion resin layer, and a sheath resin layer. However, conventional fusion resins have a problem in that streaks often occur in the fusion resin layer to be laminated, which deteriorates the adhesion between the metal and the sheath resin.

These streaks occur due to local changes in the thickness of the welding resin layer, and not only do they impair the appearance of the product, but also cracks occur in thin parts of the welding resin layer, reducing the functionality of the product.

Japanese Unexamined Patent Publication No. 81-296044 filed by the applicant of the present application discloses an ethylene-vinyl acetate copolymer of 97 to 45% by weight as a welding resin that can prevent the formation of streaks in the welding resin layer as described above. parts, styrenic polymer resin 30~
1 part by weight, 15 to 1 part by weight of an unsaturated carboxylic acid or its derivative graft-modified polyethylene, and 30 to 1 part by weight of a monovinyl aromatic hydrocarbon/olefin block copolymer elastomer. However, when a laminated metal tape is manufactured using this thermoplastic resin composition as a fusion resin, although no streaks occur in the fusion resin layer, the adhesion between the metal and resin sheath layer is not necessarily sufficient.

Therefore, it has been desired to develop an adhesive resin composition that does not cause streaks in the fusion (adhesion) resin layer and can provide excellent adhesion between the metal-resin sheath layer.

Purpose of the Invention The present invention is intended to solve the problems associated with the prior art as described above, and is capable of eliminating streaks in the fusion resin layer and providing excellent adhesion between the metal and thermoplastic resin sheath layers. The object of the present invention is to provide an adhesive resin composition that can impart properties.

Summary of the Invention The adhesive resin composition according to the present invention comprises: (a) ethylene-vinyl acetate copolymer: 96 to 45 parts by weight, (b) styrene polymer resin: 30 to 1 part by weight, (c)
Graft-modified polyethylene resin graft-modified with unsaturated carboxylic acid or its derivative = 15 to 1 part by weight, (d) Monovinyl aromatic hydrocarbon/olefin block copolymer elastomer: 20 to 1 part by weight, and (e) Ethylene. α-olefin copolymer: 20 to 1 part by weight (component (a), component (b), component (c), (d)
The total amount of component ) and component (e) is 100 parts by weight.

Detailed Description of the Invention The adhesive resin composition according to the present invention will be specifically described below.

(a) Ethylene-vinyl acetate copolymer The (a) ethylene-vinyl acetate copolymer used in the present invention is a known ethylene-vinyl acetate copolymer (EVA).
In the present invention, the melt flow rate [
MFR(E): ASTM D 1238. E] is 0.1
~50g/10min, preferably 1-30g/10min, vinyl acetate content 5-30% by weight, preferably 8-11
% by weight of ethylene-vinyl acetate copolymer is used.

When an ethylene-vinyl acetate copolymer having MFR (E) within the above range is used, an adhesive resin composition having excellent extrusion moldability and adhesiveness can be obtained.

In the present invention, (a) the ethylene-vinyl acetate copolymer is
(a) Ethylene-vinyl acetate copolymer, (b) styrene polymer resin, (c) graft modified polyethylene, (d
) monovinyl aromatic hydrocarbon/elementary olefin block copolymer elastomer and (e) ethylene/α-olefin copolymer 96 to 4 for a total of ff1100 parts by weight
It is used in an amount of 5 parts by weight, preferably 85 to 50 parts by weight.

(b) Styrene polymer resin The styrene polymer resin (b) used in the present invention includes styrene homopolymer, chlorostyrene, dichlorostyrene, methylstyrene, dimethylstyrene, α-methylstyrene, etc. and a polymer or copolymer whose main component is a styrene substituted with a nucleus or an unsaturated bond substituted at the α-position, and in the present invention, the melt flow rate [MFR (G): ASTM D
1238. G] is 0, 1 to 5 0
g/10 min, preferably 1 to 40 g/10 min of styrenic polymer. When a styrenic polymer resin having MFR (G) within the above range is used, an adhesive resin composition with excellent extrusion moldability can be obtained.

In the present invention, (b) styrenic polymer resin is (a) ethylene-vinyl acetate copolymer, (b) styrenic polymer resin, (c) graft-modified polyethylene, (d) monovinyl aromatic hydrocarbon. It is used in an amount of 30 to 1 part by weight, preferably 25 to 5 parts by weight, based on 100 parts by weight of the total amount of the olefin block copolymer elastomer and (e) ethylene/α-olefin copolymer.

(c) Graft-modified polyethylene The (c) graft-modified polyethylene used in the present invention is obtained by grafting polyethylene with a monomer selected from unsaturated carboxylic acids or derivatives thereof. Graft-modified polyethylene whose derivative has a graft-modified amount of usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight is used. Here, polyethylene is an ethylene homopolymer or ethylene and a small amount of other α-carbon atoms having 3 to 20 carbon atoms.
Olefins such as propylene, 1-butene, 4-methyl-1-pentene, l-hexene, -octene, 1-
Copolymers with decene etc., including low density, medium density and high density ones.

The reaction between polyethylene and an unsaturated carboxylic acid or a derivative thereof is generally carried out in the presence or absence of a solvent, using a radical initiator, or simply by heating. Regardless of which method is adopted, in the present invention, graft-modified polyethylene with a gel content of 10% by weight or less (as measured by decalinne solubles at 135° C.) is preferably used because it has excellent adhesive properties. When a graft-modified polyethylene having a gel content within the above range is used, an adhesive resin composition having excellent adhesion to metals can be obtained.

Further, in the present invention, the melt flow rate [MPR
(E): ASTM D 1238. E] is 0.1 to 50
A graft modified polyethylene of 0.5 to 10 g/l 0 min is used.

Specifically, the unsaturated carboxylic acids or derivatives thereof used in the graft modification of polyethylene as described above in the present invention include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, Crotonic acid, isocrotonic acid, nadic acid (trade name,
unsaturated carboxylic acids such as endocis-bicyclo[2,2,11hept-5-ene-2,3-dicarboxylic acid), or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc. Specifically, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like are used.

Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid (trade name), or their acid anhydrides are particularly preferably used.

In the present invention, (c) graft modified polyethylene is (a
) ethylene-vinyl acetate copolymer, (b) styrene polymer resin, (c) graft-modified polyethylene, (d) monovinyl aromatic hydrocarbon/olefin block copolymer elastomer, and (e) ethylene/α-olefin copolymer. 15 to 1 part by weight per 100 parts by weight of the total amount of the polymer,
Preferably it is used in an amount of 10 to 2 parts by weight.

(d) Monovinyl aromatic hydrocarbon used in the present invention.
Olefin block copolymer elastomer has the general formula (
A-B), (A-B+-A'n or (A-B←-X (wherein, A and Ao are monovinyl aromatic hydrocarbon polymer blocks, B
is an olefin polymer block; n is an integer of 1 to 5; m is an integer of 2 to 7; It is a polymer having a block structure consisting of aromatic hydrocarbon polymer blocks. Preferred monovinyl aromatic hydrocarbons are styrene and α-methylstyrene, with styrene being particularly preferred. Examples of the olefin include conjugated diolefins such as butadiene and isoprene, and α-olefins such as ethylene, propylene, and -butene. Moreover, the polymer block obtained by polymerizing the conjugated diolefin may be hydrogenated. Furthermore, block B may be a copolymer of butadiene, isoprene, etc., and styrene, α-methylstyrene, as long as olefin units are predominant. In the present invention, (d) the monovinyl aromatic hydrocarbon/olefin block copolymer elastomer has the monovinyl aromatic hydrocarbon polymer block in an amount of usually 8 to 55% by weight, preferably 10 to 35% by weight, and both Preferably, the terminal end is a monovinyl aromatic hydrocarbon polymer block. These block copolymers are manufactured and sold, for example, as Kaliflex TR and Kraton G (both trade names, manufactured by Shell Chemical Company).

In the present invention, (d) monovinyl aromatic hydrocarbon/olefin block copolymer elastomer includes (a) ethylene-vinyl acetate copolymer, (b) styrene polymer resin,
20 to 1 part by weight, preferably based on 100 parts by weight of the total amount of (c) graft-modified polyethylene, (d) monovinyl aromatic hydrocarbon/olefin block copolymer elastomer, and (e) ethylene/α-olefin copolymer. is used in an amount of 18 to 3 parts by weight.

(e) Ethylene/α-olefin copolymer The ethylene/α-olefin copolymer used in the present invention is a random copolymerization of ethylene and α-olefin, and has the following characteristics. There is.

Melt flow rate [MFR (E): ASTM D 1
238. E]: 0.1 to 50 g/10 minutes, preferably 0.3 to 30 g/10 minutes Density: 0.850 to 0.900 g/- preferably 0.8
50-0.890g/cra Ethylene content: 75-95 mol% preferably 75-9
0 mol% X-ray crystallinity = less than 30%, preferably less than 25%.

When an ethylene/α-olefin copolymer having characteristic values within the above range is used, an adhesive resin composition with excellent adhesive properties can be obtained.

α- which constitutes this ethylene/α-olefin copolymer
As the olefin, an α-olefin having 3 to 20 carbon atoms is used, and specifically, propylene, l-butene, l-
-hexene, 4-methyl-1-pentene, i-octene, 1-decene, l-tetradecene, l-octadecene, etc., and these α-olefins may be used alone or in combination with two
Used as a mixture of more than one species.

Such an ethylene/α-olefin copolymer usually has a melting point (ASTM D 3418) of 100° C. or lower.

In the present invention, (e) ethylene/α-olefin copolymer includes (a) ethylene-vinyl acetate copolymer, (b) styrene polymer resin, (c) graft modified polyethylene,
20 to 1 part by weight per 100 parts by weight of the total amount of (d) monovinyl aromatic hydrocarbon/olefin block copolymer elastomer and (e) ethylene/α-olefin copolymer.
It is used in an amount of 18 to 3 parts by weight, preferably 18 to 3 parts by weight.

The adhesive resin composition of the present invention can be prepared by mixing the components (a) to e) in amounts within the ranges described above using various known methods, such as a Henschel mixer, ■-blender, ribbon blender, tumbler blender, etc. Furthermore, it can be produced by a method in which after mixing, the mixture is melt-mixed using a screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., and then granulated or pulverized.

The adhesive resin composition of the present invention generally contains thermoplastic resins such as heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, dyes or pigments, and plasticizers such as hydrocarbon oil. The additives to be added can also be added within a range that does not impair the purpose of the present invention.

Aluminum, copper,
In order to laminate metal such as iron and thermoplastic resin such as polyamide, saponified ethylene/vinyl acetate copolymer, polyethylene, ethylene/vinyl acetate copolymer, polystyrene, polycarbonate, polyester, etc.,
A method of laminating by forming a μm-thick film of an adhesive resin composition and then setting this film between an adherend, a metal, and a thermoplastic resin and fusing them;
There are methods such as a method in which the adhesive resin composition and the thermoplastic resin as the adherend are melted in separate extruders, and then extruded from a multilayer die to perform lamination.

Effects of the Invention The adhesive resin composition according to the present invention comprises (a) an ethylene-vinyl acetate copolymer, (b) a styrene polymer resin,
It is composed of (c) graft-modified polyethylene, (d) monovinyl aromatic hydrocarbon/olefin block copolymer elastomer, and (e) ethylene/α-olefin copolymer in specific proportions. A fusion (adhesive) film with a good appearance without streaks during extrusion molding can be obtained, and excellent adhesion can be imparted between the metal and thermoplastic resin sheath layers.

Therefore, the adhesive resin composition according to the present invention can be suitably used as a fusion resin for laminate sheaths, various packaging films, and the like.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 By reacting high-density polyethylene [manufactured by Mitsui Petrochemical Industries, Ltd., HIZEX, MFR (E): 5.5 g / 10 minutes] with maleic anhydride, a maleic anhydride content of 0.5% by weight and an MFR (E ): 3. Og/10 minutes, gel content 0
．． Graft modified polyethylene of 1% or less was obtained.

To 5 parts by weight of the obtained graft-modified polyethylene, ethylene-vinyl acetate copolymer (vinyl acetate-containing ffi:
1Offin1%, MFR (E): 9. Og/10 min, hereinafter referred to as EVA) 60 parts by weight, polystyrene (trade name, Denka Styrol GP 200 S manufactured by Denki Kagaku Kogyo ■, MPR (G): 25 g/10 min, hereinafter p
s) 20 parts by weight of polybutadiene block hydrogenation of polystyrene-bolybutadiene-boristyrene block copolymer (trade name, Kraton G 1.852)
, manufactured by Shell Chemical ■, styrene content: 29% by weight) 1
0 parts by weight, and ethylene-propylene copolymer [MF
R(E): 1. Og/10 min, ethylene content 28
0 mol%, X-ray crystallinity 5%, density 0.870g
/aa] was added thereto, and the mixture was melt-kneaded and granulated using an extruder equipped with a Dalmage screw of 40IIIφ to obtain a composition (1).

The obtained composition (1) was melted at 200°C, and a press sheet having a thickness of 3IIIm was produced using a compression molding machine.

Table 1 shows the physical properties (MFR, density) of the press sheet.

Next, the composition (1
) was formed into a 50 μm thick fusing film, and after observing the presence or absence of streaks on the single film, this fusing film was used to adhere aluminum foil and polyethylene sheet under the following conditions to form a laminate. Obtained.

[Structure] AN foil/composition (1) Film/polyethylene sheet Afi foil: thickness 200 μm, width 10 cm, length 15 Composition (1) Film: thickness 50 μm, width 25 cm, length 15 cm
m polyethylene sheet: thickness 2mi, width 25IIl11,
Length 15 marks [Adhesive conditions Temperature: 200°C Pressure: 6 kg/cd Time: 3 minutes Next, a test piece for measuring adhesive strength with a width of 10 m + 1 and a length of 15 cm was cut out from this laminate with a knife. The 180° peel strength was measured at a peel rate of 200 mm/min.

The results are shown in Table 2.

Example 2 To 5 parts by weight of the maleic anhydride graft-modified high-density polyethylene used in Example 1, 70 parts by weight of EVA and PS
10 parts by weight, 10 parts by weight of Kraton G, and 5 parts by weight of ethylene-propylene copolymer were added, and the mixture was melt-kneaded and granulated in the same manner as in Example 1 to obtain a composition (2).

Press sheet physical properties (MFI?) of the obtained composition (2).

Table 1 shows the density.

Furthermore, in the same manner as in Example 1, a fusion film with a thickness of 50 μm was formed from the composition (2), and the presence or absence of streaks was observed, and the film was used to adhere an aluminum foil and a polyethylene sheet. to obtain a laminate, 18
0@Peel strength was measured.

The results are shown in Table 2.

Example 3 To 10 parts by weight of the maleic anhydride graft-modified high-density polyethylene used in Example 1, 60 parts by weight of EVA and PS
15 parts by weight, 5 parts by weight of Kraton 0, and 10 parts by weight of ethylene-propylene copolymer were added, and melt cross-wire granulation was performed in the same manner as in Example 1 to obtain a composition (3).

Table 1 shows the pressed sheet physical properties (MFR1 density) of the obtained composition (3).

Furthermore, in the same manner as in Example 1, a fusion film with a thickness of 50 μm was formed from the composition (3) and the presence or absence of streaks was observed, and the film was used to adhere an aluminum foil and a polyethylene sheet. to obtain a laminate, 18
06 peel strength was measured.

The results are shown in Table 2.

Example 4 To 5 parts by weight of the maleic anhydride graft-modified high-density polyethylene used in Example 1, 65ffi parts of EVA and P
S 15 parts by weight, Kraton G 10 parts by weight, ethylene-butene copolymer [MFR(E): 3.5 g/
10 minutes, ethylene content: 85 mol%, crystallinity 15%,
Density: 0.885 g/ad] 5 parts by weight were added, and the mixture was melt mixed and granulated in the same manner as in Example 1 to obtain a composition (4).

Table 1 shows the pressed sheet physical properties (MFR1 density) of the obtained composition (4).

Furthermore, in the same manner as in Example 1, a fusion film with a thickness of 50 μm was formed from the composition (4), and the presence or absence of streaks was observed, and the film was used to adhere an aluminum foil and a polyethylene sheet. to obtain a laminate, 18
06 peel strength was measured.

The results are shown in Table 2.

Comparative Example 1 80 parts by weight of EvA and PS were added to 5 parts by weight of the maleic anhydride graft-modified high-density polyethylene used in Example 1.
After adding 15 parts by weight, the mixture was melt mixed and granulated in the same manner as in Example 1 to obtain a composition (5).

Press sheet physical properties (MFR) of the obtained composition (5).

Table 1 shows the density.

Furthermore, in the same manner as in Example 1, a fusion film with a thickness of 50 μm was formed from the composition (5), and the presence or absence of streaks was observed, and the film was used to adhere an aluminum foil and a polyethylene sheet. to obtain a laminate, 18
00 peel strength was measured.

The results are shown in Table 2.

Comparative Example 2 To 5 parts by weight of maleic anhydride graft-modified high-density polyethylene used in Example 1, 70 parts by weight of EVA and PS
15 parts by weight and 610 parts by weight of Kraton were added, and the mixture was melt-kneaded and granulated in the same manner as in Example 1 to obtain a composition (6).

Press sheet physical properties (MPI?,
Table 1 shows the density.

Furthermore, in the same manner as in Example 1, a fusion film with a thickness of 50 μm was formed from the composition (6) and the presence or absence of streaks was observed, and the film was used to adhere an aluminum foil and a polyethylene sheet. to obtain a laminate, 18
The 0° peel strength was measured.

The results are shown in Table 2.

Comparative Example 3 To 5 parts by weight of maleic anhydride graft-modified high-density polyethylene used in Example 1, 70 parts by weight of EVA and PS
15 parts by weight and 10 parts by weight of ethylene-propylene copolymer were added and melt-kneaded and granulated in the same manner as in Example 1 to obtain a composition (7).

Table 1 shows the pressed sheet physical properties (MPR1 density) of the obtained composition (7).

Furthermore, in the same manner as in Example 1, a 50 μm thick fusion film was formed from 81 Bomono (7), and the presence or absence of streaks was observed, and the film was used to bond an aluminum foil and a polyethylene sheet. to obtain a laminate, 1
The 80° peel strength was measured.

The results are shown in Table 2.

Comparative Example 4 To 5 parts by weight of the maleic anhydride graft-modified high-density polyethylene used in Example 1, 60ffi parts of EVA, P
S 15 parts by weight, Kraton 0 10 parts by weight and high density polyethylene sheet R(E): 8.2 g/10 min, density: 0.965 g/aa, crystallinity 28
1%] was added, and the mixture was melt-kneaded and granulated in the same manner as in Example 1 to obtain a composition (8).

Table 1 shows the pressed sheet physical properties (MFR1 density) of the obtained composition (8).

Furthermore, in the same manner as in Example 1, a fusion film with a thickness of 50 μm was formed from the composition (8), and the presence or absence of streaks was observed, and the film was used to adhere an aluminum foil and a polyethylene sheet. to obtain a laminate, 18
The 0° peel strength was measured.

The results are shown in Table 2.

318-

Claims (1)

[Claims] 1) (a) Ethylene-vinyl acetate copolymer: 96 to 45 parts by weight, (b) Styrenic polymer resin: 30 to 1 part by weight, (c)
Graft-modified polyethylene graft-modified with unsaturated carboxylic acid or its derivative: 15 to 1 part by weight, (d) Monovinyl aromatic hydrocarbon/olefin block copolymer elastomer: 20 to 1 part by weight, and (e) Ethylene. α-olefin copolymer: 20 to 1 part by weight (component (a), component (b), component (c), (d)
The total amount of component () and component (e) is 100 parts by weight).