JPH10286871A - Production of laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for a laminated body in which a resin film or a metallic foil and other resin layers are laminated to each other through a co-extrusion laminating method without pre-heating or post-heating the adherend in such a manner as to have a sufficient adhesive force between the layers. SOLUTION: An adhesive layer (layer A) comprising (a) 1 to 85 wt.% of modified ethylene copolymer that is modified by unsaturated carboxylic acid, which contains 0.01 to 10 wt.% of carboxylic acid and whose density and MFR are 0.850 to 0.950 g/cm<3> and 0.05 to 50 g/10 min, respectively, (b) 1 to 59 wt.% of stickiness imparting agent and (c) 10 to 80 wt.% of a block copolymer comprising a copolymer block of a vinyl aromatic compound and a copolymer block of a conjugated diene compound or its hydro-substance and a resin layer (layer B) of a polyolefin resin or the like are laminated onto a resin film, a sheet or a metal through a co-extrusion laminating method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyolefin resin, polyester resin, saponified ethylene-vinyl acetate copolymer, polyamide resin, polycarbonate resin, polystyrene resin and acrylic resin on a resin film, sheet or metal. The present invention relates to a method for producing a laminate excellent in heat sealability, rigidity, gas permeability resistance, and interlayer adhesion by laminating a resin selected from the group consisting of the following by coextrusion lamination.

[0002]

2. Description of the Related Art Polyester films, furthermore, silica-deposited films, polypropylene films, polyamide films, saponified ethylene-vinyl acetate copolymers (EVO)
H) Films or metals represented by aluminum and copper have excellent gas permeation resistance and excellent rigidity, and are therefore widely used as food packaging materials. Even in the case of such unstretched, uniaxially or biaxially stretched film, in practical use, a polyolefin film or a polyester film is used in order to prevent deterioration at a high temperature or to impart heat sealability, and to improve gas permeation resistance. It has been proposed to laminate a saponified ethylene-vinyl acetate copolymer, polyamide, and acrylic resin with polycarbonate, polystyrene, or the like to improve rigidity. Also, for the industrial field, to prevent corrosion,
It has also been proposed to laminate a resin layer on the surface of a metal such as copper or iron.

However, when attempting to laminate the above resin film, sheet or metal and the above resin layer, an anchor coating agent is applied to the resin film, sheet or metal in advance, and then the resin to be laminated is laminated. The layers had to be extrusion laminated. Alternatively, a resin film, a sheet, or a metal and a resin layer must be bonded using a dry laminating adhesive, or a preheating step is required for lamination with a metal. In any case, such a method requires an anchor coat agent or an adhesive, and it has been difficult to simplify the lamination process.

Further, a method of coextruding and laminating a resin film, a sheet or a metal and a resin layer using low-density polyethylene as an adhesive resin layer has been proposed.
With this method, a sufficient interlayer adhesion could not be obtained.

Further, the use of a polyolefin resin into which a polar group has been introduced has been studied as an adhesive resin layer (for example, Japanese Patent Publication No. 60-28658). Even when used as a resin layer, there has been a problem that preheating and postheating of the adherend are required during coextrusion lamination.

[0006]

SUMMARY OF THE INVENTION The present invention is to solve the problems associated with the prior art as described above, and uses a specific adhesive layer to form a resin film, sheet or metal and resin layer. And without subjecting the adherend to preheating or post-heating, by co-extrusion lamination, with the object of providing a method for producing a laminate capable of producing a laminate having sufficient interlayer adhesion. I have.

[0007]

That is, the present invention relates to an ethylene-based polymer modified with an unsaturated carboxylic acid or a derivative thereof, wherein the content of the unsaturated carboxylic acid or the derivative is 0.01 to 10% by weight. , And density 0.850 ~
0.950 g / cm ³ and melt flow rate 0.0
Modified ethylene polymer (a) having a content of 5 to 50 g / 10 minutes
A block copolymer having 1 to 85% by weight, 1 to 59% by weight of a tackifier (b), at least one polymer block composed of a vinyl aromatic compound, and at least one polymer block composed of a conjugated diene compound. An adhesive layer (A) composed of 10 to 80% by weight of the unified or hydrogenated product (c) thereof
Layer) (provided that the total amount of the components (a), (b) and (c) becomes 100% by weight), and a polyolefin resin,
At least one or more thermoplastic resin layers (B layers) selected from the group consisting of polyester resins, saponified ethylene-vinyl acetate copolymers, polyamide resins, polycarbonate resins, polystyrene resins and acrylic resins. An object of the present invention is to provide a method for producing a laminate, comprising laminating on a resin film, sheet, or metal by a coextrusion lamination method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for manufacturing a laminate according to the present invention will be specifically described. The laminate obtained by the method for producing a laminate according to the present invention includes (1) a resin film, a sheet, or a metal; (2) an adhesive layer (A layer);
(3) It is composed of a thermoplastic resin layer (layer B) and can be a multilayer laminate. These layers will be described first.

(1) Resin film, sheet or metal In the present invention, an unstretched film or a uniaxial or biaxially stretched film is used as the resin film. Specifically, polyethylene terephthalate (PET), copolymer PET, Polyester resin films such as polybutylene terephthalate, polyethylene naphthalate and polycyclohexylene terephthalate; polyolefin resin films such as polypropylene and polyethylene; 6-nylon, 6,6-nylon, 6-6,6-nylon, 12-
Nylon, MXD nylon or other polyamide-based resin film, K-coated nylon film, other saponified ethylene-vinyl acetate copolymer film, and various films with silica or aluminum deposited on one or both surfaces. A film, a printed film having one side or both sides printed with various inks, or the like is used. Such a resin film is usually 5-1
It has a thickness of 00 μm and is excellent in gas permeation resistance, and is excellent in mechanical strength, moisture resistance, transparency and heat resistance.

Further, an unstretched sheet or a uniaxially or biaxially stretched sheet is used as the resin sheet. Specifically, polyethylene terephthalate (PET), copolymer PET, polybutylene terephthalate, polyethylene naphthalate, polycyclohexylene Polyester resin sheet such as terephthalate, polyolefin resin sheet such as polypropylene and polyethylene, 6-nylon, 6,6-nylon, 6-6,6-nylon, 12-
Nylon, polyamide resin sheet such as MXD nylon, K-coated nylon sheet, other ethylene-
A saponified vinyl acetate copolymer sheet, a vapor-deposited sheet in which silica or aluminum or the like is vapor-deposited on one or both surfaces on the surface of various sheets, or a printed sheet on which one or both surfaces are printed with various inks, etc. are used. Can be

The metal used in the present invention is a metal foil,
It may be plate-like or tubular, for example, copper, aluminum,
Conventionally used materials such as iron can be widely used. Further, the metal itself may be used, or kraft paper or the like may be adhered to the back surface.

(2) Adhesive layer (layer A) The adhesive layer (layer A) contains the following components (a) to (c). That is, as the component (a), the ethylene polymer is modified with an unsaturated carboxylic acid or a derivative thereof, the content of the unsaturated carboxylic acid or the derivative is 0.01 to 10% by weight, and the density is 0.85%.
0 to 0.950 g / cm ³ , melt flow rate 0.0
Modified ethylene polymer 1 to 8 having a content of 5 to 50 g / 10 minutes
5% by weight, 1 to 59% by weight of a tackifier as a component (b), and at least one polymer block mainly containing a vinyl aromatic compound as a component (c) and a conjugated diene compound as a main component. It is composed of a block copolymer having at least one polymer block or a resin composition comprising 10 to 80% by weight of a hydrogenated product thereof. However, the total amount of the components (a), (b) and (c) is 100% by weight.

(I) Modified ethylene-based polymer (a) In the present invention, the modified ethylene-based polymer (a) is defined as an ethylene-based polymer obtained by graft copolymerizing an ethylene-based polymer with an unsaturated carboxylic acid or a derivative thereof. Modified by dilution with a system polymer. A suitable ethylene polymer used for the modification has a melt flow rate of 0.05 to 50 g /
10 minutes, ethylene homopolymer having a density of 0.850 to 0.950 g / cm ³ , or ethylene and α-olefin,
It is a copolymer with vinyl ester, unsaturated carboxylic acid ester and the like. The α-olefin constituting the ethylene-α-olefin copolymer is usually an α-olefin containing no cyclic molecule having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene , 1-
Octene, 1-decene, 1-tetradecene, 1-octadecene and the like, each of which may be used alone or as a mixture of two or more. Further, two or more kinds of ethylene polymers can be used as a mixture. Specific examples include low density polyethylene (LDPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), and low crystalline ethylene-butene. -1
Random copolymer (EBM), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the like.

The unsaturated carboxylic acids or derivatives thereof used for the modification include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid R (endosis-bicyclo [2 , 2,1] Hept-5-ene-
Unsaturated carboxylic acids such as 2,3-dicarboxylic acid) or derivatives thereof, for example, acid halides, amides, imides, anhydrides, and esters. Specific examples include maleenyl chloride, maleimide, maleic anhydride, and anhydride. Citraconic acid,
Examples thereof include monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid R or acid anhydrides thereof are particularly preferable.

In order to produce the modified ethylene polymer (a), various conventionally known methods can be employed. For example, a method in which an ethylene polymer, an unsaturated carboxylic acid or a derivative thereof, and a radical generator are mixed in advance and melted by an extruder to carry out graft copolymerization, or a method in which the ethylene polymer is dissolved in a solvent and the radical generator is unsaturated. There is a method of adding a carboxylic acid or a derivative thereof and performing graft copolymerization. In any case, the reaction is preferably carried out in the presence of a radical initiator in order to graft copolymerize the unsaturated carboxylic acid or its derivative efficiently. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The usage temperature of the radical initiator is usually in the range of 0.001 to 1 part by weight based on 100 parts by weight of the ethylene polymer. Examples of the radical initiator include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide,
Di-t-butyl peroxide, 2,5-dimethyl-2,
5-di (peroxybenzoate) hexyne-3,1,
4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butyl
Butyl perisobutyrate, t-butyl per-s-octoate, t-butyl perpivalate, cumyl pervivalate and t-butyl perdiethyl acetate, and other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate There is a rate. Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,4-bis (t-butylperoxyisopropyl) benzene And the like are preferred.

When the modified ethylene polymer (a) is diluted with the same or different ethylene polymer as the ethylene polymer before the modification, the content of the unsaturated carboxylic acid or its derivative is within the above range after the dilution. Must be within.

Such a modified ethylene polymer (a)
Has an unsaturated carboxylic acid or derivative thereof content of 0.0
1 to 10% by weight, preferably 0.02 to 9% by weight, particularly preferably 0.03 to 8% by weight and a density of 0.8 to 0.8%.
50 to 0.950 g / cm ³ , preferably 0.852 to
0.948 g / cm ³ , particularly preferably 0.855 to
0.945 g / cm ³ and a melt flow rate of 0.05 to 50 g / 10 min, preferably 0.06 to 4
9 g / 10 min, particularly preferably 0.07 to 48 g / 1
0 minutes.

When the content of the unsaturated carboxylic acid or its derivative is less than the above range, the adhesiveness is not improved. On the other hand, when the content exceeds the above range, the dispersibility is reduced due to crosslinking, and the appearance of the molded article is reduced. And the adhesiveness is reduced.
Further, if the density is too low, the workability during the molding process is remarkably deteriorated, while if it is too high, the adhesive strength is so low that it cannot be put to practical use. If the melt flow rate is outside the above range, the melt viscosity is too high or too low, resulting in poor moldability and poor adhesive strength. The melt flow rate (MFR) in the present invention means a value measured at a temperature of 190 ° C. under a load of 2.16 kg for 10 minutes in accordance with JIS K7210.

(Ii) Tackifier (b) The tackifier (b) used in the present invention is an amorphous resin which is solid at ordinary temperature, among which a petroleum resin, a rosin resin, a terpene resin or a resin thereof. A hydrogenated product is preferable, and can be appropriately selected from commercially available products. Examples of the petroleum resin include an aliphatic petroleum resin, an aromatic petroleum resin, a copolymer thereof, and a hydrogenated product thereof. Specifically, as a commercially available product, Toho High Resin (Toho Petroleum Resin) Co., Ltd.), Pico Pale (Pico), Alcon P and M (Arakawa Chemical Co., Ltd.), Admarb (Idemitsu Petrochemical Co., Ltd.), Super Star Tack (Reichhold Co., Ltd.), Escolets (Esso Chemical) Co., Ltd.), Toho Petro Resin (Tonen Petroleum Resin Co., Ltd.), Heylets (Mitsui Petrochemical Co., Ltd.), Quinton (Nihon Zeon Co., Ltd.) and the like.

Examples of the rosin-based resin include natural rosin, polymerized rosin and derivatives thereof such as pentaerythroester rosin, glycerin ester rosin and hydrogenated products thereof. Specifically, gum rosin, wood rosin, Ester gum A, Persen A, Persen C (Arakawa Chemical Industries, Ltd.), pentalin A, pentalin C, Foral 105 (Rika Hercules, Inc.) and the like. As terpene resins, there are polyterpene resins, terpene phenol resins and hydrogenated products thereof. Specifically, picolite S and A (Pico), YS resin, clearon (Yasuhara Yushi Co., Ltd.) are commercially available. And the like.

In the present invention, these tackifiers can be properly used depending on the intended use. Among these tackifiers, the softening point (ring and ball method) is preferably 70 to 15.
A temperature of 0 ° C, particularly preferably 90 to 150 ° C, is used. If the softening point is too low, the adhesive strength tends to decrease, and at the same time, the melt kneading with a hydrogenated block copolymer or an ethylene-based polymer tends to be difficult. Further, in order to make the hue of the composition as close as possible to a natural color (white or colorless and transparent, prevention of yellow coloring), an aliphatic petroleum resin,
Aromatic petroleum resins or copolymers thereof are preferred, and hydrogenated products thereof are particularly preferred. The degree of hydrogenation is preferably 80% or more, more preferably 90% or more.

(Iii) Block copolymer or its hydrogenated product (c) The block copolymer or its hydrogenated product (c) used in the present invention is a block copolymer of a vinyl aromatic compound and a conjugated diene compound. It is a hydrogenated block copolymer obtained by hydrogenating the coalesced product. When the block copolymer is a polymer block composed of a vinyl aromatic compound and the block B is a polymer block composed of a conjugated diene compound, the general formulas AB, ABA, BA
In the block copolymer represented by -BA, ABABA, or the like, as a compound containing a vinyl aromatic compound constituting the polymer block portion A as a main component, for example, styrene, One or more types are selected from α-methylstyrene, vinyltoluene and the like, and among them, styrene is preferred.

Examples of the conjugated diene compound constituting the polymer block B include butadiene, isoprene,
One or more kinds are selected from 1,3-pentadiene and the like,
Among them, butadiene, isoprene and a combination thereof are preferred. The content of the polymer block composed of the vinyl aromatic compound serving as the block A is 10 to 80% by weight, preferably 10 to 70% by weight. If the content of the present polymer block is less than or greater than the above range, the adhesive strength is undesirably reduced.

The hydrogenation rate of the polymer block comprising the conjugated diene compound is generally 50% or more, preferably 80%.
Or more, more preferably 90% or more, particularly preferably 9% or more.
It is at least 5%, and a higher value is particularly preferable because the thermal stability is improved.

Block copolymer or hydrogenated product thereof (c)
Preferably has a number average molecular weight of 10,000 to 400,0.
About 00, more preferably 20,000 to 300,0.
00. If the molecular weight is too large or too small, the adhesive strength tends to decrease, and if the number average molecular weight is too large, the processability of the present composition tends to decrease.

Even if the block copolymer or its hydrogenated product (c) has a number average molecular weight of 400,000 or less, if the number average molecular weight is higher, the process oil, the liquid polybutadiene, and the number average molecular weight are 6,000. A fluidity improver selected from the following olefinic waxes is used in an amount of 1 to 4 parts by weight per 100 parts by weight of the block copolymer or its hydrogenated product (c).
By adding about 0 parts by weight, it is possible to suppress a decrease in adhesive strength and workability, which is an effective means. A block copolymer having an ABA structure is preferable. Specific examples of commercially available products include a styrene-butadiene-based hydrogenated block copolymer, "Toughtec" H type (manufactured by Asahi Kasei Corporation), and "Clayton" G1600. "Septon" 2000 type (manufactured by Kuraray Co., Ltd.) as a styrene-isoprene-based hydrogenated block copolymer, "Califlex" TR as a styrene-butadiene-based block copolymer and a styrene-isoprene-based block copolymer Type (manufactured by Shell Chemical Co., Ltd.) and Vector (manufactured by Dexico). Further, a styrene-isoprene-based hydrogenated block copolymer having an AB structure, “Septon” 1000 type (manufactured by Kuraray Co., Ltd.), “Clayton” G1700 type (manufactured by Shell Chemical Co., Ltd.), and the like can be given.

Further, two or more kinds of the above block copolymers can be used as a mixture.

(3) Preparation of composition for adhesive layer (layer A) To obtain this composition, the modified ethylene polymer (a), tackifier (b) and block copolymer Alternatively, the hydrogenated product (c) is mixed by various known methods, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or after mixing, a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer. After melt-kneading as described above, a method of granulating or pulverizing may be adopted. The amount of each of the above components is 1 to 85% by weight, preferably 2 to 83% by weight, more preferably 3 to 80% by weight, and the tackifier (b) 1 to 59% by weight of the modified ethylene polymer (a). % By weight, preferably 2-55% by weight,
More preferably, 3 to 50% by weight, and 10 to 80% by weight, preferably 10 to 78% by weight, more preferably 10 to 75% by weight of the block copolymer or its hydrogenated product (c).
% By weight. 1% by weight of modified ethylene polymer (a)
If the amount is less than 85% by weight or more than 85% by weight, the adhesive strength tends to decrease. If the amount of the tackifier (b) is less than 1% by weight, the adhesive force to each adherend decreases. The fluidity tends to be too high and the moldability tends to deteriorate, and when the block copolymer or its hydrogenated product (c)
If the amount is less than 80% by weight or less than 80% by weight, the adhesiveness tends to decrease.

Further, in addition to the above-mentioned components, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a pigment, a dye, a rust inhibitor and the like may be added to the composition, if necessary.

(4) Thermoplastic resin layer (B layer) In the present invention, as the thermoplastic resin layer (B layer), polyolefin resin, polyester resin, saponified ethylene-vinyl acetate copolymer, polyamide resin, A resin selected from a polycarbonate resin, a polystyrene resin, and an acrylic resin is used.

The polyolefin-based resin used for the thermoplastic resin layer (B layer) refers to ethylene-, propylene-, or 1-butene, which is an α-olefin having 2 to 4 carbon atoms, or a crystalline polymer containing these as a main component. It is united. Specific examples of these polyolefins include polyethylene, polypropylene, and poly-1-butene. However, these are not limited to homopolymers, and any other polyolefins having 2 to 20 carbon atoms can be used as long as the olefin is the main component. α-olefins or vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, copolymers with vinyl compounds such as styrene, and maleic anhydride, maleic acid, unsaturated carboxylic acids such as acrylic acid or A graft copolymer modified with a derivative thereof may be used. Further, these polyolefins may be a mixture. Specific examples of the polyethylene include high-pressure low-density polyethylene (LDPE), ethylene-propylene copolymer,
Ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene polymer, ethylene-1-hexene copolymer, high-density polyethylene (HDPE), ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer Polymers, ethylene-acrylate copolymers and the like can be mentioned.
Among these, LDPE, ethylene-α-olefin random copolymer, ethylene-vinyl acetate copolymer and the like are preferable because they have excellent transparency and low-temperature heat sealability,
Particularly, those having a density of 0.910 to 0.960 g / cm ³ and a melting point of 100 to 135 ° C are preferable. The melt flow rate of polyethylene is not particularly limited, but is usually 0.01 to 30 g / 1 from the viewpoint of moldability.
It is preferably 0 minutes, more preferably 0.1 to 10 g / 10 minutes.

Specific examples of the polypropylene include, for example, polypropylene (propylene homopolymer), propylene-ethylene random copolymer, propylene-ethylene-1-butene random copolymer and propylene-
Propylene random copolymers such as 1-butene random copolymer (propylene content is usually 90% or more, preferably 95% or more), propylene-ethylene block copolymer (ethylene content is usually 5 to 30% by mole), etc. No. Among these, homopolymers and random copolymers are preferable because of their excellent transparency, and particularly, the melting point is 1
A random copolymer having a temperature of 30 to 140 ° C. is preferable because of excellent heat sealing properties. The melt flow rate of propylene is not particularly limited, but is usually 0.5 to 30 g / 10 min, and more preferably 0.5 to 10 g / 1 from the viewpoint of moldability.
A range of 0 minutes is preferred.

Specific examples of the above-mentioned poly-1-butene include:
Examples thereof include 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, and 1-butene-4-methyl-1-pentene copolymer. The melt flow rate of poly-1-butene is not particularly limited, but is usually 0.01 to 100 g from the viewpoint of moldability.
/ 10 min, more preferably 0.03 to 30 g / 10 min.

The polyester used for the thermoplastic resin layer (B layer) includes terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, and naphthalene-1,4-
Or an aromatic dicarboxylic acid such as 2,6-dicarboxylic acid, an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, sebacic acid, and undecadicarboxylic acid; an alicyclic dicarboxylic acid such as hexahydroterephthalic acid; An acid component of a dicarboxylic acid of the formula (I), an alicyclic glycol such as ethylene glycol, propylene glycol, 1,4-butanediol and neopentyl glycol, an alicyclic glycol such as cyclohexanedimethanol, and bisphenol A
And a glycol component such as an aromatic dihydroxy compound such as polyethylene terephthalate (PET), copolymer PET, polybutylene terephthalate, polyethylene naphthalate, and polycyclohexine terephthalate. Particularly preferred among these is polyethylene terephthalate (PET), a thermoplastic polyester resin in which at least 80 mol% of the dicarboxylic acid component is terephthalic acid and at least 80 mol% of the glycol component is ethylene glycol.
Furthermore, copolymer PET or a mixture of PET and another polyester may be used.

The saponified ethylene-vinyl acetate copolymer used in the thermoplastic resin layer (layer B) preferably has an ethylene content of 15 to 60 mol%, more preferably 25 mol%.
An ethylene-vinyl acetate copolymer having a saponification degree of 50% by mole or more, preferably 90% or more, is used. If the ethylene content is too low, it is not preferable because it is easily decomposed by heat, is difficult to melt-mold, has poor stretchability, easily absorbs water and swells, and has poor water resistance. On the other hand, if the ethylene content is too high, the gas permeability resistance tends to decrease. Also, if the saponification degree is too low,
Gas permeation resistance tends to decrease.

The polyamide resin used for the thermoplastic resin layer (layer B) includes hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine,
1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m
-Or an aliphatic such as p-xylylenediamine, alicyclic, diamine such as aromatic and adipic acid, suberic acid,
Sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, aliphatic such as isophthalic acid, alicyclic, polyamide obtained by polycondensation with dicarboxylic acid such as aromatic,
Polyamides obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanecarboxylic acid, polyamides obtained from lactams such as ε-caprolactam and ω-laurolactam, and mixtures of copolymerized polyamides composed of these components. Is exemplified. Specifically, nylon 6, nylon 66, nylon 6
10, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/1
1 and the like. Among these, nylon 6 and nylon 66 which are excellent in melting point, rigidity and the like are preferable. Although the molecular weight is not particularly limited, the relative viscosity ηr (J
A polyamide having an IS K6810 (measured in 98% sulfuric acid) of 0.5 or more is used, and among them, a polyamide of 2.0 or more is preferable.

The polycarbonate resins used for the thermoplastic resin layer (B layer) are various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method. As dihydroxy compounds, hydroquinone, resorcinol,
4,4'-dihydroxydiphenylmethane, 4,4'-
Dihydroxydiphenylethane, 4,4'-dihydroxydiphenyl-n-butane, 4,4'-dihydroxydiphenylheptane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-2,2-
Propane (bisphenol A), 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2-propane, 4,4'-dihydroxy-3,3'-diphenyldiphenyl-2,2-propane, 4, 4′-dihydroxydichlorodiphenyl-2,2-propane, 4,4′-dihydroxydiphenyl-1,1-cyclopentane, 4,
4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4'-dihydroxydiphenylmethylphenylmethane, 4,4'-dihydroxydiphenylethylphenylmethane, 4,4'-dihydroxydiphenyl-2,
2,2-trichloro-1,1-ethane, 2,2′-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl ether, 4,
For example, 4'-dihydroxy-3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxyphenyl ether are used. 4,4 'of these
Polycarbonate using dihydroxydiphenyl-2,2-propane (bisphenol A) has mechanical performance,
It is preferable because it has excellent transparency.

The polystyrene resin used for the thermoplastic resin layer (B layer) is mainly composed of a styrene homopolymer, a copolymer of styrene and acrylonitrile, methyl (meth) acrylate, or the like, or a rubber-modified styrene thereof. Resin, specifically, polystyrene, impact-resistant polystyrene (rubber-containing polystyrene), and AS resin (SA
N), a thermoplastic resin called ABS or the like is used. Polystyrene generally has a melt flow rate of 0.1 to 50 g / 10 min, preferably 1 to 20 g / 10 min.
Minute range. If the MFR is out of the above range, the moldability tends to be inferior in any case.

The acrylic resin used for the thermoplastic resin layer (layer B) includes polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, 2-ethylhexyl polyacrylate, polymethyl methacrylate, polyacrylonitrile, Polymethacrylonitrile, methyl methacrylate-acrylonitrile copolymer, methyl methacrylate
α-methylstyrene copolymer and the like can be exemplified. Further, a styrene-acrylonitrile copolymer, a styrene-acrylonitrile-butadiene copolymer, a styrene-methyl methacrylate copolymer, or the like may be used.
Among them, polyacrylonitrile and styrene-acrylonitrile-butadiene copolymer are preferred. These acrylic resins can be appropriately selected from commercially available products, and various plasticizers, stabilizers, inorganic fillers, additives such as antistatic agents and pigments, as long as the effects of the present invention are not impaired. May be blended.

(5) Method for Producing a Laminate In the present invention, the composition constituting the adhesive layer (A layer) and the resin constituting at least one or more kinds of thermoplastic resin layers (B layers) are separately provided. Is melted by an extruder, and after melting, is separately supplied to a die having a structure of two or three or more layers.
A laminate can be manufactured by performing coextrusion lamination so that the adhesive layer (A layer) is in contact with the (1) resin film, sheet or metal. The die used here is a so-called flat die, and may be either a single-manifold type using a black box or a multi-manifold type. Alternatively, the laminate may be manufactured by performing sand lamination in which an adhesive layer (A layer) is extruded between base materials made of a resin film, a sheet, or a metal. At this time, the resin film, sheet or metal does not necessarily need to be pre-heated or post-heated.

[0041]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Embodiment 1 Ethylene-butene copolymer (density: 0.920 g / cm ³ , MFR 190 ° C.-2.16
kg: 2 g / 10 min, melting point: 124 ° C.) 45% by weight, maleic anhydride-modified ethylene-butene copolymer (maleic anhydride content: 1% by weight, MFR 190 ° C.-2.16 k)
g: 1 g / 10 min, density: 0.919 g / cm ³ , melting point: 121 ° C) 15% by weight, tackifier (aromatic hydrogenated petroleum resin, number average molecular weight: 710, specific gravity: 0.99)
8, softening point: 115 ° C) 25% by weight, hydrogenated styrene-butadiene copolymer (styrene content: 20% by weight, MF
R200 ° C-6 kg: 9.5 g / 10 min, density: 0.9
8 g / cm ³ ) The mixture was previously mixed at a blending ratio of 15% by weight with a 50-liter V-blender for 5 minutes, and the twin-screw extruder PC was used.
M30 (30mmφ, L / D = 32, Ikekai Iron Works Co., Ltd.)
180 ° C, screw rotation speed 100r
The mixture was melt-kneaded at pm and an extrusion rate of 5 kg, extruded in a string form, cooled, and cut to obtain a composition used for the adhesive layer.

This composition was used as an adhesive layer (A layer). As the resin layer (layer B), low-density polyethylene (trade name L
M38 manufactured by Mitsubishi Chemical Co., Ltd.) or polypropylene (trade name: FL25R, manufactured by Mitsubishi Chemical Co., Ltd.); polyester resin as a gas barrier resin (trade name: PET-G 676)
3, specific gravity: 1.27, intrinsic viscosity: 0.75 dl / g, manufactured by Eastman Kodak Co., Ltd., saponified ethylene-vinyl acetate copolymer (trade name: EVAL EP-G156, ethylene content: 47 mol%, density: 1.12 g / cm ³ , melting point: 160 ° C., melt index: 6.4, manufactured by Kuraray Co., Ltd.), polyamide-based resin (product name Novatec 10)
20CA2, melting point: 224 ° C., manufactured by Mitsubishi Chemical Corporation), polycarbonate (trade name: Iupilon E2000, specific gravity: 1.2, manufactured by Mitsubishi Gas Chemical Co., Ltd.), polystyrene resin (trade name: Denkastyrol HI-E-4) ,specific gravity:
1.04, melt index: 3.5, manufactured by Denki Kagaku Kogyo Co., Ltd., acrylic resin: polyacrylonitrile (trade name: Barex 3000N, specific gravity: 1.15, melt index: 3, Mitsui Toatsu Chemicals, Inc.) Was used.

In this example, the following biaxially stretched film or aluminum foil was used as the resin film, sheet or metal constituting the laminate. O-PET (stretched polyethylene terephthalate) # 1
2 (12 μm thickness) O-Ny (stretched nylon) # 15 (15 μm thickness) O-PP (stretched polypropylene) # 20 (20 μm
Thickness) O-EVOH (Saponified stretched ethylene-vinyl acetate copolymer) # 12 (12 µm thick) Al foil # 7 (7 µm thick)
30μm thick) SiO _x deposited O-PET (silica vapor deposited stretched polyethylene terephthalate adhesive surface) # 12 (stretched nylon and K coated 12μm thickness) K-Ny (adhesive surface) # 1
5 (15 μm thickness) Printing film (film with solid printing on O-PP) # 20 (20 μm thickness)

By a two-layer, two-layer co-extrusion T-die film forming method, the layer thickness of the adhesive layer (30 mmφ) / resin layer (65 mmφ) was set to 10 μm / 30 μm from the resin film, sheet or metal side. A laminate was produced at a molding temperature.

Polyester resin = 275 ° C. Polyamide resin = 250 ° C. Saponified ethylene-vinyl acetate copolymer = 230 ° C. Acrylic resin = 220 ° C. Styrene resin = 220 ° C. Polycarbonate resin = 275 ° C. Polyolefin resin = 230 ° C. The molding speed was set at 60 m / min.

The interlayer adhesion (g / 10 mm) between the resin film, sheet or metal and the thermoplastic resin layer (B layer) is expressed by J
It was measured under the following conditions in accordance with IS K-6854. Peeling width: 10 mm Peeling state: T-peel peeling Peeling temperature: 50 mm / min Measurement atmosphere temperature: 23 ° C.

Further, some applications require boil evaluation, so the following method was used. Boil treatment (1) The laminate (using Al foil) obtained by the above production method was heat-sealed in a bag shape, filled with 100 cc of the following contents, treated in steam at 100 ° C. for 30 minutes, and then heated at 23 ° C. The sample was cooled in (° C) for 3 hours.

Content: Water: vinegar: edible oil = 1: 1: 1 mixture

Boil treatment (2) The laminated body (resin multilayer film) obtained by the above-mentioned production method is heat-sealed in a bag shape, filled with water as a content, filled with 100 cc, and then treated in a thermostat at 80 ° C. for 30 minutes. And cooled at 23 ° C. (3 hours) to obtain a sample.

The following Examples and Comparative Examples were performed in the same procedure as in Example 1. Only the method for producing the composition used for the adhesive layer (A layer) is described, and the evaluation results are shown in Tables 1 and 2.

Embodiment 2 FIG. Low density polyethylene (density:
0.919 g / cm ³ , MFR 190 ° C.-2.16 k
g: 14 g / 10 min, melting point: 106 ° C.) 30% by weight, maleic anhydride-modified ethylene-butene copolymer (maleic anhydride content: 1% by weight, MFR 190 ° C.-2.16 k)
g: 1 g / 10 min, melting point: 121 ° C., density 0.919 g
/ Cm ³ ) 15% by weight, tackifier (aromatic hydrogenated petroleum resin, number average molecular weight: 860, softening point: 140 ° C.) 25
% By weight, hydrogenated styrene-butadiene copolymer (styrene content: 30% by weight, MFR 200 ° C.-5 kg: 3.5
g / 10 minutes, hydrogenation rate 98%) was mixed in advance in a blending ratio of 30% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (30 mmφ, L / D = 32, Ikekai Iron Works Co., Ltd.) ), Melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 100 rpm, and an extrusion rate of 5 kg, extruded into a string, cooled, and cut to obtain a composition.

Embodiment 3 FIG. Maleic anhydride-modified hydrogenated ethylene-butene copolymer (maleic anhydride content: 1% by weight,
Density 0.880 g / cm ³ , MFR 190 ° C-2.16
kg: 1 g / 10 min, melting point: 72 ° C) 50% by weight, tackifier (aromatic hydrogenated petroleum resin, molecular weight 710, specific gravity 0.998, softening point 115 ° C) 30% by weight, styrene-
Butadiene copolymer hydrogenated product (styrene content: 13% by weight, MFR 200 ° C-5 kg: 8 g / 10 min, hydrogenation rate 9
8%) 50 liters of V in advance with 20% by weight
Mix for 5 minutes in a mold blender and use a twin screw extruder PCM30.
(30 mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.), melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 100 rpm, and an extrusion rate of 5 kg, extruded into a string, cooled, and cut to obtain a composition. .

Embodiment 4 FIG. Maleic anhydride-modified ethylene-
Butene copolymer (maleic anhydride content: 0.4% by weight,
Density 0.880 g / cm ³ , MFR 190 ° C-2.16
kg: 4 g / 10 min, melting point: 72 ° C.) 80% by weight, tackifier (β-pinene-terpene resin, number average molecular weight 8)
20, softening point 112 ° C) 10% by weight, hydrogenated styrene-butadiene copolymer (styrene content: 29% by weight, MF
R200 ° C-5kg: 10g / 10min, hydrogenation rate 98%)
The mixture was previously mixed at a blending ratio of 10% by weight in a 50-liter V-type blender for 5 minutes, and a twin-screw extruder PCM30 (30 m
mφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.), temperature 180 ° C., screw rotation speed 100 rpm, throughput 5 k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain a composition.

Comparative Example 1 Low density polyethylene (density 0.
919 g / cm ³ , MFR 190 ° C.-2.16 kg: 1
4 g / 10 min, melting point: 106 ° C.) 45% by weight, ethylene-
Propylene copolymer (C ₃ content: 27% by weight, MFR1
90 ° C-2.16 kg: 0.7 g / 10 min, melting point: 20
C) 15% by weight, maleic anhydride-modified ethylene-butene copolymer (maleic anhydride content: 1% by weight, MFR 19
0 ° C.-2.16 kg: 1 g / 10 min, density: 0.919
g / cm ³ , melting point: 121 ° C.) The mixture was preliminarily mixed in a 50-liter V-blender at a mixing ratio of 40% by weight for 5 minutes, and a twin-screw extruder PCM30 (30 mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.) ), Melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 100 rpm, and an extrusion rate of 5 kg, extruded into a string, cooled, and cut to obtain a composition.

Comparative Example 2 Low density polyethylene (density 0.
919 g / cm ³ , MFR 190 ° C.-2.16 kg: 1
4 g / 10 min, melting point: 106 ° C.) 45% by weight, ethylene-
Propylene copolymer (C ₃ content: 27%, MFR 190
° C-2.16 kg: 0.7 g / 10 minutes, melting point: 20 ° C)
15% by weight, maleic anhydride-modified ethylene-butene copolymer (maleic anhydride content: 1% by weight, MFR 190 ° C)
-2.16 kg: 1 g / 10 min, density: 0.919 g /
cm ³ , melting point: 121 ° C.) The mixture was preliminarily mixed at a mixing ratio of 40% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (30 mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.) was used. Used, temperature 180 ° C, screw rotation speed 1
The mixture was melt-kneaded at 00 rpm and an extrusion rate of 5 kg, extruded into a string, cooled, and cut to obtain a composition. Further, 50% by weight of the resin composition obtained above was added to EVA (V208M) 5.
0% by weight was mixed in a 50-liter V-type blender for 5 minutes, and the obtained sample was evaluated in the same manner as in Example 1.

Comparative Example 3 Low density polyethylene (density 0.
919 g / cm ³ , MFR 190 ° C.-2.16 kg: 1
4 g / 10 min, melting point: 106 ° C.) 45% by weight, ethylene-
Propylene copolymer (C ₃ content: 27%, MFR 190
° C-2.16 kg: 0.7 g / 10 minutes, melting point: 20 ° C)
15% by weight, maleic anhydride-modified ethylene-butene copolymer (maleic anhydride content: 1% by weight, MFR 190 ° C)
-2.16 kg: 1 g / 10 min, density: 0.919 g /
cm ³ , melting point: 121 ° C.) The mixture was preliminarily mixed at a mixing ratio of 40% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (30 mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.) was used. Used, temperature 180 ° C, screw rotation speed 1
The mixture was melt-kneaded at 00 rpm and an extrusion rate of 5 kg, extruded into a string, cooled, and cut to obtain a composition. Further, 50% by weight of the resin composition obtained above was added to EMA (Nisseki RB420).
0) 50% by weight of 5% with a 50 liter V-blender
After mixing for 1 minute, the obtained sample was evaluated in the same manner as in Example 1.

Comparative Example 4 Ethylene-butene copolymer (density: 0.88 g / cm ³ , MFR 190 ° C.-2.16 k
g: 1 g / 10 min, melting point: 72 ° C) 50% by weight, maleic anhydride-modified ethylene-butene copolymer (maleic anhydride content: 1% by weight, MFR 190 ° C-2.16 kg: 1)
g / 10 min, density: 0.919 g / cm ³ , melting point 121
C) 20% by weight, tackifier (aromatic hydrogenated petroleum resin, number average molecular weight: 860, specific gravity: 0.999, softening point: 140 ° C.) Mix for 5 minutes in a mold blender, and twin screw extruder PC
M30 (30mmφ, L / D = 32, Ikekai Iron Works Co., Ltd.)
180 ° C, screw rotation speed 100r
The mixture was melt-kneaded at pm and an extrusion rate of 5 kg, extruded into a string, cooled, and cut to obtain a composition.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

According to the method for producing a laminate according to the present invention, (1) a resin film, a sheet or a metal
(2) an adhesive layer (A layer); and (3) a thermoplastic resin selected from a polyolefin resin, a polyester resin, a saponified ethylene-vinyl acetate copolymer, a polyamide resin, a polycarbonate resin, a polystyrene resin, and polystyrene. The layer (layer B) is laminated by a co-extrusion laminating method, so that a laminate having a sufficient interlayer adhesion can be obtained without applying an anchor coat agent in advance, and the layer can be adhered during the co-extrusion lamination. An excellent effect of not requiring preheating or postheating of the body is obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29K 23:00 B29L 9:00

Claims (1)

[Claims] An ethylene polymer is modified with an unsaturated carboxylic acid or a derivative thereof, the content of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 10% by weight, and the density is 0.850 to 0. It consists of 1 to 85% by weight of a modified ethylene polymer (a) having a melt flow rate of 950 g / cm ³ and a melt flow rate of 0.05 to 50 g / 10 minutes, 1 to 59% by weight of a tackifier (b), and a vinyl aromatic compound. A block copolymer having at least one polymer block and at least one polymer block composed of a conjugated diene compound or a hydrogenated product thereof (c) 10
Adhesive layer (A layer) consisting of up to 80% by weight (provided that the total amount of the components (a), (b) and (c) is 100% by weight), a polyolefin resin, a polyester resin, ethylene- A saponified vinyl acetate copolymer, a polyamide resin, a polycarbonate resin, a polystyrene resin, and at least one thermoplastic resin layer (B layer) selected from the group consisting of an acrylic resin are formed by coextrusion lamination with a resin. A method for producing a laminate, comprising laminating on a film, sheet or metal.