JPH11240996A - Bonding composition and multilayered structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bonding composition capable of manifesting excellent bonding properties to a polyolefin and a polyketone and good in moldability. SOLUTION: This bonding composition contains 100 pts.wt. graft copolymer prepared by grafting at least one polymerizable ethylenically unsaturated carboxylic acid or its derivative onto the backbone of a polyolefin at 0.001-0.6 wt.% graft ratio and having >=2 g/10 min melt flow rate, 0.01-1.0 pt.wt. compound having at least two primary or secondary amino groups in which at least one thereof is the primary amino group and, as necessary, <=233 pts.wt. polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an adhesive composition and a multilayer structure. More specifically, the present invention relates to an adhesive composition having excellent moldability and good adhesiveness, and a multilayer structure using the same.

[0002]

2. Description of the Prior Art Polyolefin-containing mixtures suitable for use as adhesive layers in multilayer structures are known. These adhesive mixtures are commonly referred to as tie layers. For example, U.S. Pat.
A modified polyolefin comprising (A) a graft copolymer having a polyethylene backbone grafted with at least one polymerizable ethylenically unsaturated carboxylic acid or carboxylic anhydride, and (B) a mixed resin mixture containing linear low-density polyethylene and polypropylene An adhesive mixture is disclosed.

For the purposes of the present invention, polyketones are
(A) units derived from carbon monoxide, and (b) 1
It is defined as a linear polymer having an alternating structure of units derived from one or more olefinically unsaturated compounds. Also, mixtures in which the linear polymer contains a small proportion (eg, up to 10% by weight) of the corresponding homopolymer or copolymer derived from an olefinically unsaturated compound are to be understood to fall within this definition. It is.

[0004] Such polyketones have the formula:

[0005]

Embedded image

Wherein R is independently hydrogen or a hydrocarbyl group and m is a large integer. These are disclosed in U.S. Pat. No. 3,694,412. Also, a method for producing a polyketone is described in US Pat. No. 3,694,412 and European Patent No.
No. 1014 and EP 121965. WO9 is an adhesive resin for polyketone.
This is introduced in 5/09212.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin-containing adhesive composition having a novel composition. Another object of the present invention is to provide an adhesive resin which can improve the adhesive force with polyketone and can be molded. Still another object of the present invention is to provide an adhesive resin having an excellent balance between good adhesive strength and moldability. Still other objects and advantages of the present invention will become apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention include: (A) at least one polymerizable ethylenically unsaturated carboxylic acid or derivative thereof having a graft ratio of 0 to the polyolefin backbone; Grafted at 0.001 to 0.6% by weight and melt flow rate (load 2.
16 kg, 190 ° C.) of at least 2 g / 10 min.
This is achieved by an adhesive composition characterized in that it contains 0.01 to 1.0 parts by weight of a compound having at least two primary or secondary amino groups, one of which is a primary amino group.

The polyolefin used as the backbone of the graft copolymer (A) includes, for example, polyethylene,
Examples thereof include a polyolefin resin such as polypropylene, and an ethylene-α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.
A particularly preferred example is an ethylene-α-olefin copolymer having a density of 0.850 to 0.910 and a crystallinity of 38% or less.

When the adhesive composition of the present invention is used to bind a polyolefin to a polyketone, the polyolefin used for the backbone polymer of component (A) is preferably the same as the polyolefin to be joined. For example, when polypropylene is bonded to a polyketone by the adhesive composition of the present invention, component (A) is preferably a polypropylene graft copolymer.

Examples of the polymerizable ethylenically unsaturated carboxylic acid and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, and 4-methylcyclohexene.
4-ene-1,2-dicarboxylic anhydride, bicyclo (2.
2.2) Oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2- Okusa-1,3
-Diketospiro (4.4) non-7-ene, bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic anhydride, x-methyl-norborn-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3 -Dicarboxylic anhydrides. Preferably, maleic anhydride is used.

In the graft copolymer of the component (A), the graft ratio of at least one polymerizable ethylenically unsaturated carboxylic acid or a derivative thereof to the polyolefin is 0.001 to 0.6% by weight.

In order to graft a graft monomer selected from the unsaturated carboxylic acid or a derivative thereof to a polyolefin, various conventionally known methods can be employed. For example, there is a method in which a polyolefin is melted and a graft monomer is added thereto to cause a graft reaction, or a method in which a polyolefin is dissolved in a solvent to form a solution, and a graft monomer is added thereto to cause a graft reaction. In any case, in order to carry out the graft copolymerization of the graft monomer efficiently, it is preferable to carry out the graft reaction in the presence of a radical initiator.
The grafting reaction is usually performed at a temperature of 60 to 350C. The proportion of the radical initiator used is polyolefin 10
It is usually in the range of 0.001 to 1 part by weight with respect to 0 part by weight.

Examples of the radical initiator include organic peroxides and organic polyesters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-
Dimethyl-2,5-di (peroxidebenzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide,
tert-butyl peracetate, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexyne-
3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, ter
t-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, and other azo compounds such as azobisisobutyronitrile, dimethylazo Isobutyrate is used.

Among them, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, 1,4-bis (tert-
Dialkyl peroxides such as butylperoxyisopropyl) benzene are preferred.

Here, the graft ratio refers to the weight ratio (%) of the grafted unsaturated carboxylic acid or its derivative based on the total weight of the polyolefin before grafting.
Is defined as

Methods for preparing graft copolymers are well known and may be used in any suitable manner, for example, for preparing from a polyolefin such as polypropylene and a polymerizable ethylenically unsaturated carboxylic acid or derivative thereof. Can be.

One such preferred method is that at the temperature above the melting point of the polyolefin and giving a suitable half-life of the radical initiator in the presence of a radical initiator such as an organic peroxide or hydrogen peroxide. It consists of mixing together the polyolefin and the polymerizable ethylenically unsaturated carboxylic acid or a derivative thereof. Suitable radical initiators are well known. This grafting method can be performed using a known mixing device such as a Brabender mixer, a Banbury mixer or a roll mill. Preferably, the grafting process is performed in a closed container.

A convenient method for preparing the graft copolymers is by a single or multiple screw extruder, a polyolefin forming a backbone polymer, a polymerizable ethylenically unsaturated carboxylic acid or derivative thereof, and an organic peroxide or Extrusion together with a radical initiator such as hydrogen peroxide. In this case, they may be mixed in advance and supplied to the extruder, or after feeding the trunk polymer to the extruder, feed the polymerizable ethylenically unsaturated carboxylic acid and peroxide in the middle of the extruder to perform the graft reaction. You may let it.

The melt flow rate (load: 2.16 kg, 190 ° C.) of the graft copolymer (A) is 2 g / 10
More than a minute. It is preferably at least 2 to 40 g / 10 min, particularly preferably at least 2 to 20 g / 10 min.

The polyolefin of component (B) can be a homopolymer or copolymer of ethylene or an α-olefin having 3 to 10 carbon atoms. For example, polyethylene, polypropylene, for example, having 3 carbon atoms such as butene
It may be a copolymer of at least one α-olefin comonomer having 10 to 10 and ethylene, or a copolymer of ethylene or an α-olefin having 4 to 10 carbon atoms and propylene. Component (B) is preferably the same as the polyolefin backbone polymer used to prepare component (A). That is, when the component (A) is a modified graft copolymer of a polypropylene backbone polymer, the component (B)
Is preferably polypropylene. Furthermore,
When the adhesive composition of the present invention is used for bonding a polyolefin to a polyketone, component (B) is preferably a polyolefin identical or similar to the polyolefin to be bonded.

Component (B) is an optional component, but is used in an amount of 233 parts by weight or less based on 100 parts by weight of component (A). Component (B) preferably has a melt flow rate (load 2.16 kg, 190 ° C.) of 5 to 60 g / 10 min, particularly preferably 10 to 40 g / 10 min.

Component (C) is a compound having at least two primary or secondary amino groups, at least one of which is a primary amino group. Component (C) is preferably a diamine containing two primary amino groups and up to 16 carbon atoms, with at least 2 carbon atoms between the primary amino groups. Examples of such a diamine include an aromatic skeleton linking amino groups such as phenylenediamine, 4,4′-diaminobiphenyl and di (4-aminophenyl) ether, or di (4-aminocyclohexyl) It contains a cyclic aliphatic linking skeleton such as methane or 1,4-diaminocyclooctane, or has the formula: H ₂ N (CH ₂ ) _n NH ₂ (II) (where n is an integer including 2 to 16) Acyclic terminal primary diamine). Such an expression (I
Examples of the polymethylene diamine of I) include trimethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, and hexadecamethylene diamine. Also, a diamine corresponding to a form in which an oxa group (—O—) is introduced between two adjacent methylene groups at an arbitrary position of polymethylene diamine, for example, 4,9-dioxadodecane-1,12-diamine is also used. It is preferably used.

Component (C) is used in an amount of 0.01 to 1.0 part by weight, preferably 0.01 to 0.01 part by weight, per 100 parts by weight of component (A).
Used in 6 parts by weight.

Component (C) is a graft copolymer (A)
Reacts with. Component (C) can be reacted with graft copolymer (A) in several ways. The preferred method is to react them in the melt by melt mixing them in a known mixing device such as a Brabender mixer, Banbury mixer or roll mill or twin screw extruder.

The reaction of component (C) with the graft copolymer (A) can be carried out before or simultaneously with mixing with component (B) (if used). However, it is preferred that the graft copolymer (A) first reacts with component (C) and then mixes with (B).

The adhesive composition comprising components (A), (B) and (C) can be prepared using known techniques and equipment for batch or continuous mixing.

The adhesive composition of the present invention can also contain additives conventionally used in such compositions, such as, for example, antioxidants.

The polyolefin-containing adhesive composition of the present invention is particularly suitable for bonding a polyolefin to a polyketone. Methods of using adhesive compositions to bind polyolefins to polar substrates are known, for example,
Lamination, coextrusion, extrusion lamination and coextrusion coating can be mentioned.

The present invention comprises a first layer containing a polyolefin and a second layer containing a polyketone.
Also provided is a multilayer structure in which the layers are bonded together with an interlayer of the adhesive composition of the present invention. In particular, the present invention provides multilayer structures, such as multilayer films produced by coextrusion, for example, coextrusion.

A polyolefin layer is any layer that contains a major portion of an olefin homopolymer or copolymer. Preferably, the polyolefin layer contains polyethylene or polypropylene, for example at least 70% by weight of polymerized propylene units.

The second layer contains the polyketone as described above. As mentioned above for the purposes of the present invention, polyketones are those having a selective structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefinically unsaturated compounds. Is defined as a dendritic polymer. Suitable olefinic units are those derived from, or substituted derivatives of, C ₂ -C ₁₂ alpha-olefins, or styrene or alkyl-substituted derivatives of styrene. Such olefins are preferably selected from n- alpha-olefins of C ₂ -C _5. Then, either the olefin units are derived from ethylene, or, most preferably, ethylene and one or more C ₃ -C ₆ of n- alpha-olefins, for example, particularly those derived from mixtures of propylene particularly preferred.

In these most preferred materials, it is further preferred that the molar ratio of ethylene units to C ₃ -C ₆ n-alpha-olefin units is greater than or equal to 1, preferably between 2 and 30. .

[0034] The multilayer structure according to the invention may contain further layers in addition to the three layers defined hereinbefore. For example, a five-layer structure includes a first layer of polyolefin, a second layer of the adhesive composition of the present invention, a third layer of polyketone, a fourth layer of the adhesive composition of the present invention, and a fifth layer of polyolefin. be able to.

The present invention is made by thermoforming a multilayer film or sheet in which a first layer comprising a polyolefin and a second layer comprising a polyketone are bonded together with an interlayer of the adhesive composition of the invention. Products can be provided.

[0036]

EXAMPLES The present invention will be described with reference to the following examples. Examples 1 to 12 and Comparative Examples 1 to 7 (1) As component (A), a graft copolymer used in Examples described in Tables 1 and 2 and a graft copolymer used in Comparative Examples described in Tables 3 and 4 were prepared. did.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

In Tables 1-4, MFR is the melt flow rate, MAH is maleic anhydride, and
H-PO represents maleic anhydride grafted polyethylene.

(2) 4,9-dioxadodecane-1,1
2-Diamine, LLDPE (component (B)) and the maleic anhydride-grafted polyethylene are melt-mixed at a rate shown in Tables 5 to 9 below at 210 ° C. in a 30 mmφ twin-screw extruder at a rotor speed of 270 rpm. did. Using the obtained adhesive composition, five layers of low-density polyethylene / adhesive composition / polyketone / adhesive composition / low-density polyethylene (300/100/200/100 /
(300 μm) was produced using a multilayer extruder at a molding speed of 0.5 m / min.

The obtained laminated structure was subjected to a peeling test, and the adhesive strength (N / 15 mm) of the adhesive composition of the present invention to polyketone was measured. Tables 5 to 9 show the adhesive strength between the adhesive composition of the present invention and polyketone.

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

Example 13 and Comparative Example 8 (1) Graft copolymers shown in Table 10 below were prepared as component (A).

[0050]

[Table 10] Tables 1 to 4 show the meanings of MFR, MAH and MAH-PO.
Is the same as

(2) 4,9-dioxadodecane-1,1
2-Diamine, LLDPE (component (B)) and the maleic anhydride-grafted polyethylene were melt-mixed at a rate shown in Table 11 below at 210 ° C. in a 30 mmφ twin-screw extruder at a rotor speed of 270 rpm. Using the obtained adhesive composition, 5 of low-density polyethylene / adhesive composition / polyketone / adhesive composition / low-density polyethylene was used.
Layers (in this order, 300/100/200/100/3
(00 μm) was produced at a molding speed of 0.5 m / min using a multilayer extruder.

The obtained laminated structure was subjected to a peeling test, and the adhesive strength (N / 15 mm) of the adhesive composition of the present invention to polyketone was measured. Table 11 shows the adhesive strength between the adhesive composition of the present invention and polyketone.

[0053]

[Table 11]

As is clear from the comparison between Example 13 and Comparative Example 8, the adhesive composition of Example 13 and the adhesive composition of Comparative Example 8 had almost the same content of grafted maleic anhydride. Despite this, it can be seen that the composition of Example 13 shows much better adhesive strength than the adhesive composition of Comparative Example 8.

The adhesive composition of the present invention has excellent moldability and good adhesiveness, and is particularly suitably used for adhesion between polyolefin and polyketone.

Claims (3)

[Claims] (A) at least one polymerizable ethylenically unsaturated carboxylic acid or a derivative thereof is grafted onto a polyolefin trunk at a graft ratio of 0.001 to 0.6% by weight, and a melt flow rate (load 2) .16 kg,
(C) is at least 2 g / 10 min., And (C) a compound having at least one primary or secondary amino group having at least two primary or secondary amino groups 0.01 to 1.0. An adhesive composition comprising parts by weight. 2. The adhesive composition according to claim 1, further comprising 233 parts by weight or less of polyolefin (B). 3. A multilayer structure in which a first layer comprising a polyolefin composition and a second layer comprising a polyketone composition are joined by the adhesive composition according to claim 1.