JPS60168648A - Laminate - 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 A-1 "11q Bag" D and 1 The present invention is directed to saponified ethylene-vinyl acetate copolymer (EV
(abbreviated as OH) layer).

B. Conventional technology EVOf (has good bath melt moldability, high transparency, and
Due to its excellent gas barrier properties, it has excellent performance as food containers and packaging materials, but it is still lacking in other physical properties such as rigidity and moisture resistance. . Therefore, various other resins, e.g.
It is often used in layers with polyethylene, polypropylene, polyamide, polyester, etc.

Examples of interlayer adhesives used in this case include carboxylated ethylene-vinyl acetate copolymers as disclosed in JP-A-51-67384 and JP-A-51-76366; Carboxylated ethylene-acrylic ester copolymers are well known, as seen in Japanese Patent Laid-open No. 54-101883 and Japanese Patent Application Laid-Open No. 54-110282. However, these adhesives still have insufficient adhesive strength depending on the type of resin.

Furthermore, in JP-A-50-119036, adhesives made of N,N-dimethylacrylamide-based polymer alone or a mixture of this and other thermoplastic resins are used for polyvinyl chloride, polyester, 6-nylon, etc. 1 Although it is disclosed that it exhibits excellent adhesion to vinylon, acrylic polymers, and polypropylene, there is no explanation that it is useful as an interlayer adhesive when manufacturing a laminate having an EVOH layer. do not have.

C1 Structure, purpose, and effects of the present invention The present invention is an EVC
In the laminate having the JH layer, the one-part adhesive contains 100 parts by weight of an olefin (co)polymer and the olefin (co)polymer.
This is a laminate in which chill groups R2 and R3 are alkyl groups having 1 to 4 carbon atoms in 100 parts by weight of the co)polymer.

The interlayer adhesive used in the present invention has excellent melt flowability and moldability, and the resulting laminate also has excellent peel strength, as is clear from the Examples described below.

D8 More detailed description of the present invention The (co)polymer having a structural unit represented by +CH+-CR''+ and represented by 0NR2R3 used in the present invention is +CH2-
cR1+CO is 2R3 (5 parts, lζ2. R8 is the same as above) unit is 5
It is a polymer or copolymer having 0 to 100 molti, preferably 70 to 100 molti, particularly preferably 85 to 100 molti.

Kono (co) M Combined 1d:, -General formula CH2-CB'
C0NR2R'' (R1, B2, BB are the same as above) alone, or by copolymerizing this compound with other copolymerizable monomers.

General formula CF12 Formula RICONR2R3 (However, R1,
R2 and R3 are the same as above),
N,N''-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide.

N,N-methylethyl acrylamide, various N,N-
In addition to those in which the alkyl groups of R2 and R3 are of the same kind, such as dipropylacrylamide and various N, N-dibutylacrylamide, there are also those of different kinds. Among these compounds, N,N-dimethylacrylamide and N,N-diethylacrylamide are preferred.

Furthermore, if the number of alkyl carbon atoms in both R2 and R3 exceeds 5, the adhesiveness may become insufficient, so it is necessary that the number of alkyl carbon atoms in both R2 and R3 be 4 or less.

Examples of the heteropolymerized components with these seven polymers include olefins such as Eva, ethylene, propylene, and imbutylene, as well as styrene, vinyl acetate, various acrylic esters, and various methacrylic esters. However, the content of the copolymer component is preferably within a range 1, for example, 30 mole or less, so that the effects of the present invention are not impaired.

The above homopolymer and/or copolymer thereof is produced by a known method, and its molecular weight is not particularly limited, but considering adhesiveness, miscibility, melt flowability, moldability, etc. , those having a molecular weight of 5,000 to 10,000 are preferable, and those having a molecular weight of 10,000 to 30,000 are particularly preferable.

In addition, in the present invention, the olefin-based (co)polymer is
Olefin polymers or copolymers, especially ethylene polymers or copolymers, such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-imbutylene copolymers, ethylene-vinyl carboxylate copolymers ( Examples of copolymerization components include vinyl formate,
Vinyl acetate.

vinyl propionate, vinyl butyrate, etc.) and/or their saponified products, and ethylene-(meth)acrylic rs ester copolymers (copolymerization components include methyl acrylate, ethyl acrylate, acrylic (37-n-butyl) ,
methyl methacrylate, ethyl methacrylate, etc.), among which ethylene-vinyl acetate comonomer (
(hereinafter abbreviated as EVA) and ethylene-acrylated ethyl copolymer (hereinafter abbreviated as EEA) are suitable.0EvA is 1 to 60% by weight of the vinyl acetate component, preferably 5% by weight.
-50% by weight, meltintex (hereinafter abbreviated as M) is preferably 0.1 to 3,009,710 minutes, and a part of the vinyl acetate component (for example, 0.1 to 9
(0 mol%) can also be used for one-time use. W
Preferably, fi2A contains 5 to 50% by weight of ethyl acrylate component and has an MI of 0.1 to 1009/10 minutes.

It has a structural unit represented by , for example, a method of melt-kneading in a twin-screw extruder, rolls, ) (with the latter being 0.3 to 5
0 parts by weight need to be mixed 0 preferably 0.5-30
In the present invention, the EVOH is not particularly limited, but considering gas barrier properties, melt moldability, etc., the ethylene component is preferably 20 to 55 moles, vinyl acetate, etc. It is preferable that the saponification degree of the components is 90 molti or more.

Further, in the present invention, the laminate is at least EVOH
It means a laminate having layers, for example, EVOE layer / thermal layer heavy thermoplastic resin layer plastic resin layer 1 EVOH layer / thermoplastic resin layer (thermoplastic resins may be of the same type or different types). layer/EVOH layer/thermal plastic resin layer/EVOH layer, etc., and the mixture used in the present invention described above is highly effective as an adhesive between these layers.

Other examples include a laminate consisting of a gvoi layer/thermosetting resin layer, a laminate consisting of an EvOH layer/inorganic material (e.g. glass, ceramics, etc.), an EVOH layer/gold M (aluminum, copper, silver, gold). , iron, tinplate, steel, etc.), h: VOH layer/thermoplastic resin 1m/metal, thermoplastic resin layer/EVO1'1 layer/gold maple, EVOH/metal/
A thermoplastic resin layer, an EVOH layer/metal/HVOH layer laminate, and an EVOH layer/EVOH layer laminate are also one embodiment of the laminated body of the present invention. Here, as the thermoplastic resin, various saturated polyesters represented by polyethylene terephthalate and polybutylene terephthalate, various polyamides represented by 6-nylon and 6.6-nylon, various polyolefins represented by polyethylene and polypropylene, Polystyrene, polyvinyl chloride, vinylidene chloride polymer, polycarbonate,
A wide range of polymeric materials can be mentioned, such as polymethyl methacrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, acrylonitrile polymer, and ionomer resin. Among these, saturated polyester, polyamide, and polypropylene are preferred in consideration of adhesiveness, moldability, and gas barrier properties.

The thickness of each layer of the laminate can be arbitrarily selected depending on requirements such as performance and economy.

In addition, the shape of the laminate can be a film, sheet, pipe or other profile extruded product, blow molded product or various other molded products depending on the materials used. Examples of the method include a coextrusion method, an extrusion lamination method, a dry lamination method, and a thermocompression bonding method using a press.

In addition, as for the method of using the above-mentioned mixture as an interlayer adhesive between these layers, the best method is to use a Monri compound between each layer.
Either the OH layer or the resin layer laminated with the EVOH layer,
Alternatively, it can also be used with internal pressure applied to both layers. Also,
Depending on the form of use, this mixture may contain heat stabilizers, antioxidants, anti-blocking agents, slip agents, antistatic agents, etc.
It is a good idea to add coloring agents and the like.

The laminate obtained by the present invention has extremely good adhesion between the laminate materials, and also has excellent gas barrier performance of E; , useful as packaging materials.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples in any way.

Examples 1 to 9 and Comparative Examples 1 to 3 Preparation of adhesive mixtures (1), (II) and (■1) Ethylene-vinyl acetate copolymer (vinyl acetate content 28%
The compounds shown in Table 1 were mixed for 5 minutes at 150° C. using a 3-inch roll in the proportions shown in Table 1 per 10,000 weight of a 40 mol saponified product (MI 18 F/10 minutes) using a 3-inch roll.

Preparation of adhesive mixture (IV)% (V) and (Vl) The compounds shown in Table 1 were added to 100 parts by weight of ethylene-vinyl acetate copolymer (vinyl acetate content 10% by weight, M13F/10 minutes). The mixture was mixed at 140° C. for 5 minutes using a 3-inch roll at the ratio shown in 1.

Preparation of adhesive mixtures (■)% (■) and (IX) The compounds shown in Table 1 were added to 100 parts by weight of ethylene-ethyl acrylate copolymer (ethyl acrylate content 18% by weight, MI6f/10 minutes). The mixtures were mixed at 150° for 5 minutes using a 3-inch roll at the blending ratio shown in Table 1.

Below is a blank table. 1 Next, 40 mol of the adhesive mixtures (1) to (IX) and an etele/-vinyl acetate copolymer (vinyl acetate content: 28 folds, M118f/10 min) without a compound were prepared. Saponified 4-Nuclide (X), ethylene-vinyl acetate copolymer (total amount of vinyl acetate 10 times!!, MI3f/10 minutes) 03)
, ethylene-ethyl acrylate copolymer (ethyl acrylate content 18% by weight, MI6 f710 min) (M) was used as the intermediate layer (B) (thickness 50μ), and INVOH
m (A) 32 moles of ethylene, saponification degree of 995 moles, thickness 25 μm, A2: ethylene 41 moles, saponification degree of 995 moles, thickness of 25 μm, and as the other resin layer (C), Cll polyethylene terephthalate 75 μm, C2 polyamide (6-nylon) - 100μC3 polypropylene
4011 to obtain a laminate having a three-layer structure of A/B/C.

Table 2 shows the glabella peel strength of the obtained laminate.

Further, the oxygen permeability of each of the laminates in Examples 1 to 9 was 10 CC/rl·24 hr-atm or less, and the gas barrier properties were good.

Patent applicant RiRashi Co., Ltd. Representative Patent Attorney Ken Honda

Claims (1)

[Scope of Claims] (1) In a laminate having a saponified ethylene-vinyl acetate copolymer layer, the interlayer adhesive comprises 100 parts by weight of an olefin (co)polymer and
has a structural unit represented by hydrogen or a methyl group (R2 represents an alkyl group having 1 to 4 carbon atoms)
A laminate comprising a mixture consisting of 0.3 to 50 parts by weight of a polymer. The (co)polymer is N,N-dimethylacrylamide (
The laminate according to claim 1, which is a co-polymer. (8) The laminate according to claim 1, wherein the olefin (co)polymer is an ethylene-vinyl acetate copolymer. (4) The laminate according to claim 1, wherein the olefin (co)polymer is an ethylene-ethyl acrylate copolymer.