JPS58203041A - 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 In detail, the present invention relates to a treetop unit suitable for the sheet-top pooling method.

Currently, it is used as a packaging container for food and other items.

Various f#'' fat-rich acid forms have been proposed, but the production method for these is generally the sheet futaming method because acid form equipment is inexpensive and acid form processing is easy. 6.

In such a forming method, holiskiren is mainly used as the material for the sheet because of its good formability.

In recent years, there has been a tendency for barrier properties to be required for resin-shaped products such as cups and trays as the contents have diversified. The purpose of the tree invention is to create a polystyrene layer and...
Do you have a high barrier property with a saponified vinyl acetate copolymer layer? A body in a rod? cT lies in providing
: By molding the layered body of the invention, it is possible to obtain food packaging containers such as cups and trays that have high parity resistance.

By the way, the present inventor has discovered that in order to laminate a film or sheet of polystyrene and a film or sheet of saponified equilene-vinyl acetate copolymer, for example, a method of laminating with an adhesive applied thereto, or a method of laminating between the two is used. Resin set 5y
thing? Attempts were made to laminate one or more plug layers, apply adhesive bonding, or co-extrusion.

However, I decided to use an adhesive to laminate a long polystyrene film or sheet and a laminate or sheet of a saponified vinyl acetate copolymer using an adhesive layer. There is a problem that peeling of the layer or cutting of the layer occurs.

In addition, even in the case of the above resin composition, which is formed into an orange layer, adhesively bonded, and co-extruded into a door shape, there is no one that can obtain sufficient adhesive strength, and it is There is a problem that peeling occurs.

As a result of various studies regarding the problems of upper Be, the inventor of the tree found that the vinyl acetate content ranged from 5 to 50.
'□ftB% of ethylene-vinyl acetate 1 combination fk pilgrimage 2011% to 80 units, polyolefin 20% polyolefin made by combining 1 senjuren type unsaturated car with carbonyl group → ftB% A composition of 8 DI [1 ml] is strongly adhesively bonded to the saponified Ie 3 layer of polystyrene and enylene-vinyl acetate copolymer.

Furthermore, when polystyrene and equilene-vinyl acetate polymer saponified product Y-$ was extruded and fermented into a sheet through the adhesive composition layer, it was discovered that the three were strongly adhered, and based on this knowledge, This completely prevents the present invention.

The above invention will be described in more detail below.

First, the laminate of the present invention will be explained with reference to the drawings.

As shown in the figure, polystyrene 111, a vinyl acetate content of 5i-1% to 50%, and an ethylene-vinyl acetate #aggregate resin of 201% to 8°iV have a carbonyl group. Single unit? Adhesive @ Qi 11m composition (hereinafter referred to as “adhesive 1
It is abbreviated as "composition." ) 2 Table 2 and ethylene-vinyl acetate combined saponified material theory (hereinafter abbreviated as "saponified material layer") 3 It is a layer consisting of three layers sequentially laminated.

Next, to give an example of an 8-layer laminate of another aspect of the laminate of the present invention, as shown in FIG. Three layers of material 112 and saponified material 3 are sequentially laminated, and then on top of the above saponified material 3, tiFl1, Kumiyoshi 2 and polystyrene layer 1 are sequentially laminated. ) may be used as a Wabetsu structure.

Five layers of multi-layered coextrusion were used in the case of Go and Uegide, but the number of layers other than F, which was laminated in the order of polystyrene layer, adhesive benisho gauze tube, and saponified layer, etc. Isn't it driven by the above? , an appropriate layer configuration may be used.

tt

In the above-mentioned Kihatsu 813, examples of polystyrene used in polystyrene are f, GPF reskiren,
High impact polystyrene, medium impact polystyrene 18w can be used.

Next, father, in the above-mentioned invention, is there one set of contact materials, etc.? The constituent vinyl acetate copolymer resin having a vinyl acetate content of 511 to 50 tt% can be, for example, one obtained by polymerization using a known free catalyst polymerization method.

In addition, if the combined total of ethylene-vinyl acetate in the adhesive composition layer in the present invention is less than 2 (LIR), the adhesive force between the adhesive composition layer and the polystyrene layer becomes weak, and the adhesive strength of the adhesive composition layer and the polystyrene layer becomes weaker. If the combined content exceeds 80% and qbPl, the suitability for molding and processing deteriorates. Therefore, in the present invention, the total amount of ethylene-vinyl acetate copolymer is preferably 2011% to 8%.

Next, we have also published a method of graft-polymerizing an ethyne-based unsaturated monomer having a carbonyl group, for example, a method of grafting reaction in a solution state (for example, Japanese Patent Publication No. 4a-15422). ), method of graft reaction in molten state (for example, Japanese Patent Publication No. 43-
27121), other methods in which the graft reaction is carried out in a slurry state, and methods in which graft reaction is carried out in a slurry state,
Raft reaction method (for example, Tokkosho, !13-185
It is possible to use those obtained by a weighing rod method such as (see Publication No. 22).

In addition, in the present invention, the formula having a narbonyl group ≦ Ren-based unsaturated phosphor tetramer? If the amount of oligolefin combined with the grafting group is less than 20% by electric quantity, the adhesive force between the adhesive-assembled protective layer and the saponified layer becomes weak, and the carbonyl group? When the polyolefin obtained by polymerizing the two-type unsaturated monomer Keglat becomes more than 80%, the adhesion between the adhesive compound base and the boris-surene layer becomes weak, and therefore, the present invention Teha, carbonyl group-containing Ekirenheifu 4-type Japanese monomer Kr body keg → Futohayabusa combined polyolefin is 20 to 1eS ~ 80!
1m section is preferable.

Next, examples of the carbonyl group-containing monomers in the present invention include carboxylic acids,
A carbonyl (1) group based on a carboxylate, a carboxylic anhydride, a carboxylic ester, a carboxylic acid amide or imide, an aldehyde, a ketone, etc. alone or in Schiff/
(-CfN) group; hydroxy group; ether; Suitable examples thereof are as follows.

A, engineering method Ren-based unsaturated carboxylic acids such as nialic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, q-norbornene-2,3-dicarboxylic acid, etc. °□ B, equilene-based insomniac carboxylic anhydride: maleic anhydride, citraconic anhydride, 5-turbotumene-2,3-dicarboxylic anhydride, tetrahydrophthalanhydride.

・、;、Dimanent esters: ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, mono- or di-ethyl maleate, vinyl fn-acid,
Vinyl propionate, propyl γ-hydroxy methacrylate, ethyl β-hydroxy acrylate, glycidyl acrylate, glycidyl methacrylate, β-N-ethylaminoethyl acrylate, and the like.

D, Engineering≦Renically unsaturated amide or imide: Acrylamide, methacrylamide, maleimide, etc.

E, unsaturated fulldehyde, L, methacrolein, vinyl methyl ketone, vinyl butyl ketone, etc.

In the present invention, among the above-mentioned monomers, ethylene-based unmelted carboxylic acids or ethylene-based unmelted carboxylic anhydrides are particularly preferred; Or it can be used in combination with other single rods.

In addition, the oligoolefins in the present invention include polyolefins such as polyolefins such as polyolefins, ethylene-alpha olefin copolymers polypropylene, polybutene, and polyisoprene, and polydiolefins such as polybutadiene and polyisoprene, or copolymers thereof. etc. can be used.

Next, in the present invention, is there a saponified layer? As the constituting saponified product of ethylene-vinyl acetate comonomer containing 120 to 50 moles of ethylene and having a degree of saponification of 90% la, known ones can be used, and in the present invention, When the ethylene content is 20 mol% or less, moisture resistance and water resistance are poor.
If the content is more than 50 mol, the barrier properties will deteriorate, so the content of equilene is preferably 20 to 50 mol.

In addition, since the barrier properties deteriorate if the degree of saponification is 90% or less, the degree of saponification must be 90% or more.

Furthermore, in the above-mentioned present invention, as an example of a problem that prevents the polystyrene layer, the adhesive composition layer, and the saponified material layer from being further laminated, What?
Polypropylene, olipropylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate combination, ethylene-methacrylic acid combination, ethylene-vinyl acetate combination, ethylene-vinyl acetate combination 14 Combined saponified product, -1-thousand-a-olefin combination elastomer, 1-thousand-butadiene-arylonitrile combination,
Polyamide, polycarbonate, polysulfone, polyacetal,
Volume 1,000 methacrylate, oliphenylene oxide,
Polyurethane, polyethylene terephthalate, polybutylene terephthalate.

Next, to explain the integrated manufacturing method of the present invention, there are various manufacturing methods. A method of forming a three-layer adhesive bond by layering a single sheet and film wN of each g゛/tl'' shin and then heating and pressuring them together, the father suggested the following: There is a method in which a coextrusion film 2 of each resin material to be used as a saponified layer and a saponified material layer is prepared, and then a polystyrene film or sheet constituting polystyrene is attached to the laminated film with an adhesive.

The heating method used in the present invention includes heat treatment using an induction heating roll, heat treatment by blowing hot air from a dryer, heat treatment using flame, etc.
The heat treatment is preferably carried out at a temperature of 120°C to 250°C.

In addition, in the present invention, the laminate of 5@ hinoki moromi as shown in FIG. 2 can be produced by coextrusion method etc. The temperature required for discharging is 150°C to 250°C, preferably 180°C to
The temperature is 240°C.

Also, regarding the laminate according to the present invention, its composition is three layers: a polystyrene layer, an adhesive 4Ji compound layer, and a saponified layer. The basic view structure is used, and in addition to this, lFj neat
, - or another combination can be arbitrarily set (but in this case, it is possible to use any method such as a method of laminating using a continuous adhesive, or an extrusion lamination method, etc.). be able to.

Next, what about the laminate of the present invention? To give a detailed description of the craftsmanship methods used, for example, there are % vacuum forming method, pressurized air acid forming method, vacuum pressure sand casting method, etc. In addition, Form Fill Seal a (F
Fs2) v

Is the laminate obtained by the present invention polystyrene? Adhesive 1 Composition layer 1 It can be strongly bonded only through the layer 1, and it also has good drawing W oiliness and has high barrier properties without peeling in the acid form. Various T+' 1ltli containers such as trays? It dances with supply.

In addition, this vF canister has good slipperiness on the outer and inner surfaces, and has anti-corrosion barrier properties for miso, soy sauce, tethered, juice, margarine, putter, and excrement. It can be used in a variety of ways, such as armored containers for food poisoning, official containers for pharmaceutical packaging, etc.

Next, the present invention will be described in more detail with reference to Examples.

Implementation f! A1 800μ high impact polystyrene sheet, vinyl acetate content 2871%, melt index 1B,
t/10 minutes, work ≦ Ren-vinyl acetate 1 combined resin 5
0 Ju Ayu staff and melt index 1.89-/10 minutes,
ft] [[], 905 maleic anhydride t 0.3
Low-density polyester combined with 1% graft ≦ Polyurethane 5011% composition film? 3
0 μ laminated, and then a saponified film containing 60 mol % of polyvinyl acetate and 60 mol% of polyvinyl acetate was added.
The adhesive strength between each layer of this three-layered laminate was determined by applying heat to the adhesive (92%) by passing it through a Teflon-treated induction roll (temperature = 190°C) for 17 μN (Fig. 1). When sound measurements were taken, the adhesive strength between the Oris-Elene layer and the adhesive composition layer was 1800cm/15mm, and the adhesive strength between the adjoining split-knitted material layer and saponified material 1 was 13009-w/j5mm width. C Example 2 Low index 10.5y, /lo min, specific gravity 10t Calhei Impact Boris Senshin (manufactured by Shin Nippon Ketsu Kagaku ■, Estyrene H-60) was used as 11 ferene sip, containing vinyl acetate. Rate 26 Military F 4, Nord Index 185'/10 Min Ethylene-Acid Resistant Vinyl Copolymer Resin 5Q1i Polishing%, Melt Index 1.8'
) 710 minutes, ratio t c, 9 [15 maleic anhydride [1,31N! Low-density polyethylene + 8'l graft-polymerized with 50% fat and adhesive side set Eey-, containing 33 mol of ethylene, 995 mol% of carbon ratio, 1 point 180 The ethylene-vinyl acetate #1 was combined into a saponified saponified layer at ℃, and the co-extruded sheet was prepared as shown in Figure 12.

■For each layer, use 500μ of Po-11 styrene and sound! 1:I
The p layer is 30μ and the saponified layer is 40μ.

The pressing W concentration was 22D"Ck. The adhesion force of each sieve of this coextruded sheet was kfA, l-i plus one ζ, 7?
Chie 7ka is 15 D O! ;'w / 15 ffl width, 1 set of glue layer - saponide Naruma's common name is 130
0≠v, -/15 intoxication.

In addition, although the seams were subjected to pressure-air molding, no peeling between layers or film breakage occurred, and the molding conditions were good.

Example 3 Vinyl acetate content 28N on 800μ high impact polystyrene sheet 1! jt'l Melt Index 18P/1 [] minutes Equilene-Vinyl Acetate Co-enriched body examination 7011%, Melt Index 1.11/10 minutes, ratio i! ' 0.9 [ ] 5 maleic anhydride u7X
A composite film 2 containing 30-% of low-density olefin resin grafted with t0.3i1% and a thickness of 20 μm, Ff4 L, and an elastomer-vinyl acetate film N A 17μ layer of combined saponified film 3 (ethylene content 30 molar, degree of saponification 992%) was laminated, and further hot water with a melt index of 1.8P/1[]9 minutes with a specific gravity of 0905, 1 maleic acid added, %, low-density polyethylene resin film Ak 20 μ thick, and Sara 2・Gsu 26.5 (
Product name: Thickness 671, μ oriemolene/horizakaized vinylidene/polynylene product)
Induction TJV heat roll (temperature: 1
After heating to 90°C, adhesive welding was performed (Fig. 13).

When the adhesive strength between each layer of this laminate was measured, the adhesive strength between the polyskirene 1-adhesive composition layers was 15[IO5'
w/15wi mountain? The adhesion strength between the tl1 composition layer and the saponified layer is 13 [TD carp/15mm width, saponified layer and monomaleic anhydride? The layers of low-strength polyethylene that are grafted together cannot be separated.

In addition, Saranex 26, a low-density polyethylene grafted with maleic anhydride, could not be peeled off.Also, the sheet was searched for using compressed air and acid, but there was no peeling of the floor or ψ breakage. This did not occur and the molding condition was good.

[Brief explanation of the drawing]

41 FIG. 1 is a cross-sectional view showing the composition of the 1 body of the invention 7,
Figures 2 and 3 are cross-sectional views showing another embodiment of the laminate of the present invention. １・・・・・・・・・・・・、F ll S 壬れし庖 2・
・・・・・・・・・・・・Contact agent M3 initial layer 3・・・・・・
・・・・・・Saponification R layer patent applicant Dai Nippon Printing Co., Ltd. Agent Patent attorney Atsumi Konishi

Claims (1)

[Claims] (Ilf Listyrene heat, acetic acid and two people, content of 5 to 1% to 50 layers of exhaust resin-vinyl acetate #1 combined resin 20 tons of carbonyl) Based on the intended enylene-based non-containing monomer, polyprefin grafted with graft polymerization, an adhesion compound 1 containing 20 to 80 to 1%, and 120 to 120 to [ O
A laminate formed by logging three layers of the saponified material layer of mole and saponification IJ'90 or more in the above-mentioned pus. (2.O11 styrene layer, vinyl acetate content 51%) [50% vinyl acetate #polymer tank, from 20% to 8O1, ethylene-based insomnia containing carbonyl group] Monotonic body?Graft east aligned O°1
'Olefin is blended at a ratio of 8 D f f j mo from 20 city F section, and it contains a barrel adhesive, a protective layer, and enylene! '2
0 to 10 moles, saponified 1"49% of ethylene over
Five layers: a saponified vinyl acetate copolymer layer, the above adhesive composition layer, and the above saponification inducing layer? The laminate was stacked one on top of the other.