GB2040223A - Laminate with improved inter- laminate adhesion - Google Patents

Laminate with improved inter- laminate adhesion Download PDF

Info

Publication number
GB2040223A
GB2040223A GB7944020A GB7944020A GB2040223A GB 2040223 A GB2040223 A GB 2040223A GB 7944020 A GB7944020 A GB 7944020A GB 7944020 A GB7944020 A GB 7944020A GB 2040223 A GB2040223 A GB 2040223A
Authority
GB
United Kingdom
Prior art keywords
layer
polymers
block copolymer
styrene
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB7944020A
Other versions
GB2040223B (en
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP16002178A external-priority patent/JPS5587551A/en
Priority claimed from JP3221579A external-priority patent/JPS55125175A/en
Priority claimed from JP8010479A external-priority patent/JPS564797A/en
Application filed by Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Publication of GB2040223A publication Critical patent/GB2040223A/en
Application granted granted Critical
Publication of GB2040223B publication Critical patent/GB2040223B/en
Expired legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2325/00—Polymers of vinyl-aromatic compounds, e.g. polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2377/00—Polyamides

Landscapes

  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A multi-layer laminate comprises at least one A-B double layer structure in which layer A is an olefin polymer, polyamide polymer, thermoplastic polyester polymer, acrylate polymer, polyether polymer, polycarbonate polymer, polyurethane polymer, acrylonitrile polymer, vinylidene chloride polymer, thermosetting resin, vulcanized rubber, glass or paper, and layer B is mainly a modified block copolymer in which an unsaturated carboxylic acid or its derivative is grafted on a styrene- butadiene block copolymer. Laminates which are gas barriers and steam resistant are provided (a) when layer A is a gas barrier material eg a polyamide, and layer B contains at least 65% by weight of styrene and so has a resinous character, (b) when layer A is a gas barrier material adhered via layer B to a further layer C which is aluminum or a general purpose resin eg a polyolefin.

Description

SPECIFICATION Laminate This invention relates to a novel laminate. More particularly, this invention relates to a laminate improved in interlaminar adhesion.
Hitherto, a number of attempts have been made to prepare various laminates either by bonding different materials to each other with the aim of giving the laminates the advantages of both materials or by putting one material between layers of another material with the aim of compensating the fault of the outer layer material. As materials for such laminates, there are used metallic foils such as aluminum foil or copper foil, paper and cellophane, as well as various thermoplastic resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyethylene terephthalate, nylon, polycarbonate, polystyrene, high impact polystyrene, polyvinylidene chloride, ABS resin, and the like. These laminates are used in the form of a sheet, film, blow-molded article or the like.
These laminates are generally prepared by bonding sheets or films of the same material or different materials with a binder or by co-extruding the same material or different materials without using any binder.
Sometimes, however, a sufficient adhesion effect cannot be obtained with some kinds of materials to be laminated or some combinations of materials to be laminated. Particularly when a laminate is prepared by co-extrusion without using any binder, materials lacking mutual adhesion cannot be used. Therefore, when it is intended to prepare a laminate from materials lacking mutual adhesion by co-extrusion, a material having adhesiveness to both the materials is used as an adhesive layer. As such an adhesive material, there are used, for example, ethylene-vinyl acetate copolymer, monomer resin, styrene-butadiene block copolymer and the like. However, these materials still have problems in that adhesion effects are not necessarily sufficient when some kinds of materials are co-extruded and the resulting laminates are inferior in durability of adhesion, water-resistance, etc.
The present inventors have studied these problems to find that a modified block copolymer in which an unsaturated carboxylic acid or its derivative is grafted on a styrene-butadiene block copolymer is quite excellent in adhesion to various materials and suitable for use in laminates.
According to this invention, there is provided a multi-layer laminate comprising at least one A-B double layer structure, characterized in that said layer A is a layer comprising at least one material selected from olefin polymers, polyamide polymers, thermoplastic polyester polymers, acrylate polymers, polyether polymers, polycarbonate polymers, polyurethane polymers, acrylonitrile polymers, vinylidene chloride polymers, thermosetting resins, vulcanized rubbers, glass and papers and said layer B is a layer comprising mainly a modified block copolymer in which an unsaturated carboxylic acid or its derivative is grafted on a styrene-butadiene block copolymer.
The modified block copolymer in which an unsaturated carboxylic acid or its derivative is grafted on a styrene-butadiene block copolymer (hereinafter referred to as "modified block copolymer") which forms the layer B in this invention will be mentioned below. The styrene-butadiene block copolymer (hereinafter referred to as "block copolymer") used as a base for said modified block copolymer has at least one, preferably two or more, polymer blocks composed mainly of styrene and at least one polymer block composed mainly of butadiene. In said block copolymer, the weight ratio of styrene to butadiene is preferably within the range of 10/90-90/10, more preferably 20/80-90/10, most preferably 20/80-85/15.In the polymer block composed mainly of styrene of said block copolymer, the weight ratio of styrene to butadiene is preferably within the range of 100/0-60/40, more preferably 100/0-80/20, most preferably 100/0, and the distribution of the minor constituent butadiene in the molecular chain may be any of the random, tapered (the monomer constituent increases or decreases along the molecular chain) and partially block-wise distributions or a combination thereof. In the polymer block composed mainly of butadiene, the weight ratio of styrene to butadiene is preferably within the range of 0/100-40/60, more preferably 0/100-30/70, and the distribution of minor constituent styrene in the molecular chain may be any of the random, tapered and partially block-wise distributions or a combination thereof.
In this invention, the weight ratio of the polymer block composed mainly of styrene to the polymer block composed mainly of butadiene is preferably in the range of 10/90-90/10, more preferably 15/85-85/15.
When said block copolymer contains two or more polymer blocks composed mainly of styrene ortwo or more polymer blocks composed mainly of butadiene, each of the blocks may be identical or different in structure.
A part of the styrene constituting the block copolymer of this invention may be replaced by other vinyl or vinylidene aromatic compounds such as a-methylstyrene, vinyltoluene or the like, so long as the characteristic properties of the block copolymer are not changed.
Said block copolymer has preferably a number average molecular weight of 10,000 - 1,000,000, more preferably 20,000 - 500,000, most preferably 30,000 - 300,000. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably within the range of 1.01 -10, more preferably 1.01 - 5.
The molecular structure of said block copolymer may be any of the straight chain structure, branched chain structure, radial structure and their combinations.
The above-mentioned various limitations on block copolymer are very important in order for said block copolymer to have a sufficient ability of adhesion to other materials after it is modified.
The block copolymer used in this invention is usually obtained by anionic-block copolymerizing styrene and butadiene in an inert hydrocarbon solvent such as hexane, cyclohexane, benzene,toluene or the like in the presence of an organolithium compound such as butyllithium as a polymerization catalyst. It is also possible to prepare a branched or radial block copolymer by reacting the block copolymer having an active lithium end obtained by said method, with a polyfunctional coupling agent such as carbon tetrachloride, silicon tetrachloride or the like. Any block copolymers obtained by any preparation methods other than the above may be used as a base for the modified block copolymer of this invention, unless they exceed the above-mentioned limits.
Said block copolymer may be used not only alone but also in combination of two or more. Examples of such combination include a combination of two or more styrene-butadiene block copolymers having different molecular weights, a combination of two or more styrene-butadiene block copolymers different in styrene content, a combination of styrene-butadiene block copolymers different in block structure, i.e. a styrene-butadiene block copolymer, the block structure of which is of styrene-butadiene type, and a styrene-butadiene block copolymer, the block structure of which is of styrene-butadiene-styrene type, and other combinations.
As the styrene-butadiene block copolymer used as a base for the modified block copolymer used in the laminate of this invention, straight chain block copolymers containing two polymer blocks composed mainly of styrene and two polymer blocks composed mainly of butadiene are particularly preferable, taking the processability at the time of lamination into consideration.
Styrene-isoprene block copolymers cannot be used as a base for the modified block copolymer used in this invention, because if they are used, the modified block copolymer obtained tends to undergo deterioration due to thermal history and its application to uses of laminate has a problem.
Examples of the unsaturated carboxylic acid which is grafted on the block copolymer of this invention to form the modified block copolymer include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid, cis-4-cyclohexene-1 ,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1 ]-5-heptene-2,3dicarboxylic acid and the like, and, as their derivatives, there may be mentioned acid anhydrides, esters, acid amides, dicarboxylic acid imides and the like of these carboxylic acids, among which dicarboxylic acid anhydrides are preferable and maleic anhydride is particularly preferable.
The content of unsaturated carboxylic acid or its derivative in the modified block copolymer of this invention is preferably 0.05 - 5% by weight. If it is less than 0.05% by weight the improvement of adhesion is hardly observable, and if it exceeds 5% by weight the adhesion is not significantly greater than that obtained by using a smaller amount of the modifier. In order to keep the flow property of modified block copolymer comparable to that of unmodified block copolymer, the content of unsaturated carboxylic acid or its derivative is more preferably in the range of 0.05 - 2% by weight In order to prevent foaming from occurring at the time of melt-processing due to the absorbed atmospheric water in the modified block copolymer, said content is most preferably in the range of 0.05 - 1% by weight.
Although the modified block copolymer used in this invention has a small content of unsaturated carboxylic acid or its derivative as mentioned above, it is greatly improved in adhesion as compared with unmodified block copolymer, and other properties such as melt flow property, solubility in solvent, etc. are substantially the same as those of unmodified block copolymer so that it can be processed under substantially the same conditions as in the prior techniques. This is a characteristic feature of this invention.
The fact that grafting the unsaturated carboxylic acid or its derivative falling in the range of this invention on a styrene-butadiene block copolymer is effective for obtaining a polymer useful as an adhesive layer has not be predicted from the prior knowledge at all.
The modified block copolymer of this invention can be produced by grafting an unsaturated carboxylic acid or its derivative on said block copolymer in the molten state or the solution state with or without a radical initiator. Although the process for producing the modified block copolymer is not particularly limited in this invention, some production processes are not desirable which give a modified block copolymer containing an undesirable component such as gel or the like or give a modified block copolymer, the melt viscosity of which increases so markedly as to lower the processability. One of the preferable processes is to react a block copolymer with an unsaturated carboxylic acid or its derivative in an extruder under such melt mixing conditions as to generate substantially no radical.
The modified block copolymers for forming the layer B in this invention may be used not only alone but also in combination of two or more. In the layer B, the modified block copolymer is preferably contained in a proportion of 60% by weight, more preferably 75% by weight, most preferably nearly 100% by weight for the sake of retainjng adhesion. Into the modified block copolymer of layer B may be incorporated antioxidant, stabilizer, ultraviolet absorber, colorant and the like. Further, various thermoplastic resins, unvulcanized rubber, plasticizer and other additives may also be incorporated thereinto, so long as they do not adversely affect the adhesion of the modified block copolymer.
On the other hand, in this invention, the layer A forming a multi-layer laminate comprising at least one A-B double layer structure together with the layer B composed mainly of the modified block copolymer is a layer comprising at least one material selected from the group consisting of olefin polymers, polyamide polymers, thermoplastic polyester polymers, acrylate polymers, polyether polymers, polycarbonate polymers, polyurethane polymers, acrylonitrile polymers, vinylidene chloride polymers, thermosetting resins, vulcanized rubbers, glass and papers. The modified block copolymer contained in layer B of this invention has an excellent adhesion to any of these materials for forming the layer A.
The term "olefin polymers" used herein means homopolymers of olefin monomers such as ethylene, propylene, 1 -butene, 2-butene, iso-butene, 1 3-butadiene and the like; copolymers of two or more different olefin monomers; copolymers of said olefin monomers and other monomers; and modified products of these polymers. Examples of said homopolymers of olefin monomers include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene, 1,2-polybutadiene and the like. Examples of said copolymers include ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer and the like.Examples of said modified products include ionomer (ion-cross-linked ethylenemethacrylic acid copolymer), chlorosulfonated polyethylene, chlorinated polyethylene and the like.
The term "polyamide polymers" used herein means polycondensates of diamines and dicarboxylic acids, polycondensates of aminocarboxylic acids, and ring-opened polymers of cyclic lactams. Examples of said polyamide polymers include nylon 6, nylon 6,6, nylon 11, nylon 12, nylon 6-nylon 6,6 copolymer and the like.
The term "thermoplastic polyester polymers" used herein means polycondensates of saturated dicarboxylic acids and saturated diols, and ring-opened polymers of cyclic lactones. Their examples include polyethylene terephthalate, polybutylene terephthalate, polycaprolactone and the like.
The term "acrylate polymers" used herein means homopolymers and copolymers of acrylic esters or methacrylic esters. Their examples include polymethyl methacrylate, polybutyl methacrylate, methyl methacrylate-methyl acrylate copolymer, and the like.
The term "polyether polymers" used herein means polymers having ether linkages in molecule. Their examples include polyacetal, polyethylene oxide, polypropylene oxide, polyphenylene ether and the like.
The term "polycarbonate polymers" used herein means polymers obtained by the reaction of Bisphenol A with phosgene or diphenyl carbonate.
The term "polyurethane polymers" used herein means thermoplastic polymers having urethane linkages in molecule. They include polyaddition products of diisocyanates and diols.
The term "acrylonitrile polymers" used herein means homopolymers of acrylonitrile or methacrylonitrile and copolymers of acrylonitrile or methacrylonitrile with other monomers. Examples thereof include acrylonitrile-methyl acrylate copolymer, polyacrylonitrile and the like.
The term "vinylidene chloride polymers" used herein means homopolymer of vinylidene chloride and copolymers of vinylidene chloride and other monomers.
The term "thermosetting resins" used herein means resins curable upon heating such as phenolic resin, alkyl resin, epoxy resin, unsaturated polyester resin, amino resin, urea resin and the like.
The term "vulcanized rubber" used herein means vulcanized products of natural rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, polychloroprene rubber and compositions of these rubbers and various fillers.
The term "papers" include materials generally called paper as well as "Cellophane" (Registered Trade Mark) and parchment paper (vegetable parchment).
The laminate of this invention is a multi-layer laminate comprising at least one A-B double layer structure.
When the multi-layer laminate has three or more layers, a layer or layers other than the double layer must be materials which can adhere to layer A or layer B. Particularly, layer B has a good adhesion to various materials, so that it is useful as an adhesive layer when combined with other materials to give a laminate of A-B-C three layers.
Examples of the materials for use in layer C and adherable to layer B include olefin polymers, styrene polymers (they include homopolymer of styrene and copolymers of styrene and other monomers, and their examples include polystyrene, high impact polystyrene, styrene-acrylonitrile copolymer, ABS resin and MBS resin), polyamide polymers, thermoplastic polyester polymers, acrylate polymers, polyether polymers, polycarbonate polymers, acrylonitrile polymers, vinyl chloride polymers [homopolymer of vinyl chloride and copolymers of vinyl chloride and other monomers (soft products containing a plasticizer are also included)], vinylidene chloride polymers, various thermosetting resins, various vulcanized rubbers, glass, papers, metals such as aluminum, brass, copper, tin and the like, wood, woven fabrics, non-woven fabrics and the like.
As mentioned above, the modified block copolymer used in layer B has adhesiveness to very many kinds of materials, so that multi-layer laminates of various combinations, which have hitherto been difficult to obtain, can be obtained by using said layer B as an adhesive layer, which is another characteristic feature of this invention.
For example, a three-layer laminate having a gas barrier property and a steam barrier property, being excellent in mechanical strength and having a sufficient interlaminar adhesion can be obtained by using, in this invention, the so-called gas barrier type material such as polyamide polymer (for example, nylon 6, nylon 6,6 or the like), polyethylene terephthalate, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinylidene chloride or the like as layer A, using layer B as an adhesive layer, and using aluminum or a general purpose resin such as polyethylene, polypropylene, polystyrene, high impact polystyrene or the like as layer C.The laminate of this invention obtained by combining said gas barrier type material with a general purpose resin or aluminum is excellent in interlaminar adhesion, whereas the use of hitherto known adhesive or adhesive polymer did not always give a sufficient interlaminar adhesion which was problem from a practical point of view. The modified block copolymer of this invention has an excellent adhesion to both the layers, so that it gives a useful laminate.
Further, in this invention, the modified block copolymer of layer B is resinous when the base styrene-butadiene block copolymer has a styrene content of 65% by weight or more and preferably 70% by weight or more. Thus, by using, in an A-B two-layer laminate, a gas barrier polymer such as nylon 6, nylon 6,6, polyethylene terephthalate, ethylene-vinyl alcohol copolymer or the like as layer A and the above-mentioned resinous modified block copolymer as layer B, there can be obtained a laminate having a two-layer structure, having a gas barrier property and a steam barrier property and being excellent in mechanical strengths such as impact strength.
As the process for producing these laminates, any of the processes generally employed can be utilized.
Examples of the processes which may be used include extrusion lamination process which comprises forming the modified block copolymer used in this invention into a hot molten film with an extruder, and subsequently pressing and bonding the film onto a substrate material; co-extrusion process which comprises heating and melting the modified block copolymer of this invention and a substrate in separate extruders and then laminating them in a multi-layer die; a process which comprises previously forming the modified block copolymer of this invention into a film or a sheet, putting it on a substrate and then heating and pressing the resulting assembly by means of a hot press or the like to bond the film or sheet to the substrate; hot lamination process which comprises heating and melting the modified block copolymer of this invention, and subsequently coating it onto a film-formed substrate by extrusion method, casting method or the like; dry lamination process which comprises dissolving the modified block copolymer of this invention in a solvent, coating the solution onto a substrate, evaporating off the solvent and then heating and pressing the assembly to bond the modified block copolymer to the substrate; wet lamination process which comprises using a latex obtained by dispersing the modified block copolymer of this invention in water by use of an appropriate emulsifier; and the like, though other processes may also be employed.
Among the processes mentioned above, hot melt bonding processes such as extrusion lamination, co-extrusion, hot lamination, pressing and the like are particularly preferable from a viewpoint of easiness of bonding operation, because the modified block copolymer of this invention exhibits a sufficient bonding strength if a pressure of 0.1 - 100 kg/cm2 is applied thereto at a temperature of 100" - 280"C for a period of about 2 seconds to 20 minutes.Dry lamination process is also one of the preferable processes, because the modified block copolymer of this invention is quite readily soluble in general purpose solvents such as toluene, xylene, cyclohexane, tetrahydrofuran, butyl acetate and the like and gives low viscosity solutions at a concentration of 2 - 70% As the material for forming these laminates, surface-treated materials may also be used for the sake of enhancing adhesion.
The amount of modified block copolymer used in the laminates may be such that the laminates can have a sufficient performance of adhesion. However, when the modified block copolymer is used for the purpose of giving the laminates a special function such as impact resistance, flexibility or the like, an amount enough to display the function is necessary.
The laminates obtained by the process of this invention can be put to wide uses including package film in the form of a film or sheet and co-extruded double layer materials for moldings such as blow molding, vacuum forming and air-pressure forming.
A few examples are shown below, but this invention is not limited thereto.
Example 1 By the procedure mentioned below, there was obtained a modified block copolymer in which maleic anhydride was grafted on a styrene-butadiene copolymer. It had a butadiene-styrene-butadiene-styrene block, a styrene content of 38% by weight and a number average molecular weight of 60,000.
To 100 parts by weight of said styrene-butadiene copolymer were added 1.5 parts by weight of maleic anhydride and 0.2 part by weight of phenothiazine, and they were uniformly mixed by means of a mixer.
The mixture was fed to a single screw extruder [screw diameter (D) = 40 mm, L/D = 24 (L: screw length), full-flighted screw] in an atmosphere of nitrogen and subjected to maleinization reaction at a cylinder temperature of 200"C. The unreacted maleic anhydride was removed from the obtained polymer under a reduced pressure. Results of analyses were: melt index (condition G) 7.2, toluene-insoluble fraction 0.05% by weight, and amount of maleic an hydride grafted 0.70% by weight. This modified block copolymer is referred to as sample A.
On the other hand, maleic anhydride was grafted on a block copolymer having a styrene-butadienestyrene block, a styrene content of 80% by weight and a number average molecular weight of 90,000 in an extruder in the same manner as above to obtain a modified block copolymer, which is referred to as sample B. Sample B had a melt index of 3.1 (condition G) and contained 0.08% by weight of toluene-insoluble fraction. The amount of maleic anhydride grafted was 0.87% by weight.
Samples A and B were independently formed into a sheet having a thickness of 0.3 mm. The sheets were heated and pressed with various materials shown in Table 1 by means of a press, and the peeling strength was measured according to JIS-K-6854. The results are shown in Table 1. As shown in Table 1, the laminates of the invention had an excellent adhesion.
Comparative Example 1 Laminates were prepared by repeating the procedure of Example 1, except that the same copolymer as that before the modification with maleic acid in Example 1 (referred to hereinafter as unmodified polymer) was used in the process for making sample A in Example 1. Their peeling strengths were measured by the same procedure as in Example 1 to obtain the results shown in Table 1.
TABLE 1 Peeling strength (kg/25 mm) Substrate Unmodified Sample A polymer of Sample B (Example 1) sample A (Example 1) (Comparative Example 1) High density polyethylene (HDPE) 4.0 2.1 3.6 Polypropylene (PP) 4.5 1.2 3.8 Polyvinylidene chloride (PVDC) 3.9 0.3 3.2 Nylon 6 (N-6) 8.2 1.5 8.6 Nylon 6,6 (N-6,6) 9.3 1.3 10.3 Polyethyleneterephthalate (PET) 6.5 0.2 6.0 Polybutyleneterephthalate (PBT) 6.9 0.4 5.5 Polymethyl methacrylate (PMMA)5.5 1.7 4.6 Ethylene-vinyl acetate copolymer (EVA) 5.0 3.0 4.3 Ethylene-vinyl alcohol copolymer (EVAL) 6.6 1.4 6.8 Polycarbonate (PC) 4.0 2.3 2.9 lonomer resin 8.5 2.6 Polyphenylene ether (PPE) 7.2 2.5 Polyurethane (PU) 6.6 2.4 Ethylene methacrylic acid copolymer (EMAA) 9.5 6.6 "Cellophane" Unmeasurable (Registered Trade Mark) (substrate 3.6 was broken) Unmeasurable Kraft paper (substrate 6.6 was broken) Phenolic resin 8.? 2.1 Vulcanized rubber composition 9.5 5.0 (SBR 1712 contained) Example 2 and Comparative Example 2 By using a 45-mm extruder, a 40-mm extruder and a 45-mm extruder, co-extrusion of three layers of nylon 6/sample A/high impact polystyrene and three layers of ethylene-vinyl alcohol copolymer/sample B/high impact polystyrene was conducted. For comparison, the same co-extrusion was conducted using the copolymers before the modification of samples A and B. As a result, the interlaminer strengths (peeling strength) were as shown in Table 2. The conditions of extrusion of individual resins were as shown in Tables 3and4.
TABLE 2 No. Example 2-1 Example 2-2 Comparative Comparative Item Example 2-1 Example 2-2 Layer A N-6 EVAL N-6 EVAL Structure Adhesive Unmodified Unmodified of polymer Sample A Sample B polymer of polymer of laminate (layer B) sample A sample B Layer C HIPS HIPS HIPS HIPS Peeling strength (gr/25 mm) 1,000 800 125 150 Peeling surface Layer LayerA/ LayerA/ Layer Layer B Layer B Layer B Layer B Note: N-6 : Nylon 6 EVAL : Ethylene-vinyl alcohol copolymer HIPS :High impact polystyrene TABLE 3 The co-extrusion conditions in Example 2-1 and Comparative Example 2-1 Cylinder Die Layer Polymer Extruder temperature temperature (mm P() ( C) ( C) A N-6 45 180-230 230 B Sample A or its 40 150 - 200 230 unmodified polymer C HIPS 45 150-200 230 TABLE 4 The co-extrusion conditions in Example 2-2 and Comparative Example 2-2 Cylinder Die Layer Polymer Extruder temperature temperature (mm ) ( C) ( C) A EVAL 45 170-200 210 B Sampie B or its 40 150-200 210 unmodified polymer C HIPS 45 150-200 210 Example 3 and Comparative Example 3 Sample A and, for comparison, the styrene-butadiene block copolymer before the modification of sample A were formed into sheets having a thickness of 0.5 mm by use of a hot press.The sheet was put between soft glass and aluminum and placed in an oven kept at 150"C for 20 minutes under a load of 0.1 kg/cm2 to obtain a three-layer laminate. The peeling strength of this sample was measured to obtain the result shown in Table 5.
As shown in Table 5, the laminate of Example 3 prepared from modified block copolymer is markedly improved in interlaminar peeling strength as compared with the laminate of Comparative Example 3 perpared from unmodified block copolymer. This demonstrates that the modified block copolymer of this invention has an excellent adhesion to glass.
TABLE 5 No.
Item Example 3 Comparative Example 3 Layer A Glass Glass Structure of Adhesive polymer Sample A Unmodified polymer of laminate (layer B) Sample A Layer C Aluminum Aluminum Peeling strength (kg/25 mm) 12.8 4.3 Peeling surface Layer A/Layer B Layer A/Layer B Example 4 and Comparative Example 4 By using the commercially available styrene-conjugated diene block copolymers (c-g) shown in Table 6 and the tentatively prepared styrene-butadiene block copolymers (h-i) shown in Table 7, modified block copolymers (C-l) were produced by grafting maleic anhydride thereon by the same procedure as employed in the production of sample A. Analysis values were as shown in Tables 6 and 7.
By using the modified block copolymers C-I as an adhesive layer, the verious polyamide polymers shown in Table 8 or the various polyester polymers shown in Table 9 were bonded to other materials to obtain laminates. The bonding was carried out by pressing the materials at a temperature of 200"C under a pressure of 20 kg/cm2 by means of a hot press. Peeling strengths of these laminates were measured according to JIS-K-6854 to obtain the results shown in Tables 8 and 9. For comparison, the results in the cases using unmodified block copolymers as adhesive layer are also shown in Tables 8 and 9.
As shown in Tables 8 and 9, the modified block copolymers of this invention have an excellent adhesion to polyamide polymers and polyester polymers, so that, in the peeling test of laminates, the bonding strength between the adhesive layer and the polyamide or polyester polymer is sometimes greater than the bonding strength between adhesive layer and another material and peeling takes place between adhesive layer and another material. In contrast to it, the unmodified block copolymers shown in Comparative Examples exhibit only a slight adhesion to the polyamide or polyester polymers.
TABLE 6 Symbol c d e f g Styrene- Styrene- Styrene- Styrene- Styrene Kind butadiene butadiene butadiene butadiene isoprene copolymer copolymer copolymer copolymer copolymer Unmodi- Trade name Kraton Solprene Tufdene Kraton fied block 1102 (1) T-4014 (2) KR-01 (3) 2003 (4) 1107 (5) compolymer Styrene content 28 40 80 25 14 (% by wt.) Melt index 6.7 5.2 5.3 1.8 9.6 (g/10 min.) Symbol C D E F G Amount of Modified maleic an- 1.20 0.50 0.83 0.23 0.56 block hydride grafted copolymer (% by wt.) Melt index 3.5 4.0 3.1 1.0 9.8 (g/10 min.) Notes: (1) Manufactured by Shell Co.
(2) Manufactured by Phillips Corp.
(3) Manufactured by Phillips Corp.
(4) Manufactrued by Asahi Kasei Kogyo K.K.
(5) Manufactrued by Shell Co.
TABLE 7 Symbol h Kind Styrene-butadiene Styrene-butadiene copolymer copolymer Arrangement B-S1-B2-S2 S1-B1-S2 of blocks B1 = 10% ([B]/[S] = 8/2, S1 = S2 = 15% Unmodi- Structure Weight, (1) random) (styrene only) fied of structure block polymer and monomer S1 = 25% ([B]/[[S] = 5/20, B1 = 70% co- contents of random) (butadiene only) polymer each block B2 = 40% ([B]/[S] = 32/8, Micro-structure of B1: random) 1,4-cis bond = 21% 1,2-vinyl bond = 30% S2 = 25% ([B]/[S] = 5/20, random) Styrene content 50 30 (% by wt.) Melt index (g/10 min.) 8.3 1.3 Symbol H Modified block co- Amount of maleic acid 0.73 0.36 polymer grafted (% bywt.) Melt index (g/10 min.) 6.2 1.1 Notes: (1) Bun : Polymer block composed mainly of butadiene (n represents the order along molecular chain) Polymer block composed mainly of styrene.
[B] : Content of butadiene (weight % based on total polymer).
[S] . Content of styrene (weight % based on total polymer).
TABLE 8 No.
Item Example 4-1 Example 4-2 Example 4-3 Example 4-4 Layer A (polyamide) N-6 N-6,6 N-12 N-6 Structure Adhesive layer C C D E of polymer (layer B) laminate Layer C HIPS HIPS HDPE HIPS Peeling strength 16.3 14.5 5.8 10.3 Results (kg/25 mm) of peeling test Peeling surface Layer A/ Layer Al Layer B/ Layer A/ Layer B Layer B Layer C Layer B (Abbreviations) N-6 .Nylon 6 (unstretched sheet having a thickness of 0.2 mm) N-6,6 : Nylon 6,6 (unstretched sheet having a thickness of 0.2 mm) N-12 : Nylon 12 (unstretched sheet having a thickness of 0.2 mm) HIPS : High impact polystyrene (a sheet having a thickness of 1.0 mm) HDPE : High density polyethylene (a sheet having a thickness of 1.0 mm) TABLE 8 (Cont'd) Example 4-5 Example 4-6 Example 4-7 Comparative Comparative Comparative Comparative Example 4-1 Example 4-2 Example 4-3 Example 4-4 N-6 N-6 N-6 N-6 N-12 N-6 N-6 F H I c d e h HDPE HIPS HDPE HIPS HDPE HIPS HIPS 4.5 9.5 4.3 0.7 0.5 0.1 0.1 Layer A/ Layer A/ Layer B/ Layer A/ Layer A/ Layer A/ Layer A/ Layer B Layer B Layer C Layer B Layer B Layer B Layer B TABLE 9 No.
Item Example 4-8 Example 4-9 Example 4-10 Layer A (thermoplastic PET PET PET polyester) Structure of laminate Adhesive layer plymer C D E (layer B) Layer C HDPE HIPS HDPE Peeling strength 4.8 3.8 3.1 Results of (kg/25 mm) peeling test Peeling surface Layer awl Layer awl Layer awl LayerB LayerB LayerB (Abbreviations) PET : Polyethylene terephthalate (a sheet having a thickness of 0.3 mm) PBT . Polybutyleneterephthalate (a sheet having a thickness of 0.3 mm) HDPE : High density polyethylene (a sheet having a thickness of 1.0 mm) HIPS : High impact polystyrene (a sheet having a thickness of 1.0 mm) PP :Polypropylene (a sheet having a thickness of 0.5 mm) TABLE 9 (Cont'd) Example 4-11 Example 4-12 Comparative Comparative Example 4-5 Example 4-6 PET PBT PET PBT F S d d PP HIPS HDPE HDPE 5.3 5.2 0.05 0.1 Layer Layer Layer A/ Layer Layer B Layer B Layer B Layer B Example Sand Comparative Example 5 Laminates were prepared by using the samples shown in Table 10 in the same manner as in Example 4 or Comparative Example 4. In order to examine the maintenance of their peeling strengths, the samples were allowed to stand in an oven kept at 150"C for 3 hours and then their peeling strengths were measured. The results are shown in Table 10.
As shown in Table 10, laminates prepared from the modified block copolymers containing butadiene as conjugated diene component can sufficiently retain their peeling strength. However, as shown in Comparative Example 5-2 in Table 10, the use of styrene-isoprene block copolymer (sample G) results in a marked decrease of peeling strength, which is a problem from a practical point of view.
TABLE 10 No.
Item Example 5-1 Example 5-2 Comparative Comparative Example 5-1 Example 5-2 Layer A (polyamide) N-6 N-6 N-6 N-6 Structure Adhesive layer polymer C E c G of (layer B) laminate Layer C Aluminum Aluminum Aluminum Aluminum Peeling strength 15.8 10.5 0.7 10.8 Before (kg/25 mm) heating Peeling Layer A/ Layer A/ Layer Al Layer Al Results of surface Layer B Layer B Layer B Layer B peeling test Peeling strength 14.8 9.7 0.4 4.5 After (kg/25 mm) heating Peeling Layer awl Layer awl Layer Layer N surface Layer B Layer B Layer B Layer B Maintenance of 94 92 57 42 peeling strength (%) Example 6 and Comparative Example 6 Sample A was formed into a hot molten film by use of a 25-mm extruder (single screw, UD = 22, full-flighted screw) and a T die (200-mm width, lip distance 0.2 mm). Immediately, it was put between a polyacrylonitrile resin sheet (BAREX 210, manufactured by Vistron-Lonza) and a high density polyethylene sheet (Suntec B 470 S, manufactured by Asahi Kasei) and bonded under pressure by applying a pressure of 30 kg/cm2 between the cooling roll and the nip roll to obtain a three-layer sheet of polyacrylonitrile resin/modified block copolymer/high density polyethylene. Peeling strength of this three-layer sheet was measured to obtain the results shown in Table 11.For comparison, a three-layer sheet of polyacrylonitrile resin (BAREX 210, manufactured by Vistron-Lonza)/styrene-butadiene block copolymer/high density polyethylene (Suntec B 470 S, manufactured by Asahi Kasei) was prepared by the same procedure as above, using a styrene-butadiene block copolymer which was the same as the polymer before the modification of Sample A. Peeling strength of this three-layer sheet was measured to obtain the results shown in Table 11.
As shown in Table 11, the modified block copolymer of this invention has an excellent adhesion to polyacrylonitrile resin, whereas the block copolymer before the modification used in Comparative Example 6 has no sufficient adhesion to polyacrylonitrile resin.
TABLE 11 No.
Item Example 6 Comparative Example 6 Layer A BAREX 210 BAREX 210 Structure Adhesive layer polymer Sample A Polymer before modifiof laminate (layer B) cation of sample A Layer C HDPE HDPE Peeling strength (kg/25 mm) 5.0 1.0 Peeling surface Layer A/Layer B Layer A/Layer B Examples 7-8 and Comparative Examples 7-8 Sample A was formed into a 0.5-mm sheet by use of a hot press. This sheet was put between a parchment paper (manufactured by Asahi Kasei K.K.) and a high density polyethylene sheet (Suntec B 470 S, manufactured by Asahi Kasei K.K.) and bonded by applying a pressure of 50 kg/cm2 by means of a hot press kept at 1200C for 2 minutes. Thus, a three-layer sheet of parchment paper/modified block copolymer/high density polyethylene was prepared (Example 7).
On the other hand, a three-layer sheet of parchment paper (manufactured by Asahi Kasei K.K.)/modified block copolymer/high density polyethylene (Suntec B470 S, manufactured by Asahi Kasei K.K.) was prepared by the same procedure as above by using sample B (Example 8).
Further, for comparison, three-layer sheets were prepared by repeating the procedure of Example 7, except that the styrene-butadiene block copolymer before modification of sample A (Comparative Example 7) or an ionomer resin (Copolene, manufactured by Asahi Dow K.K.) (Comparative Example 8) was used as an adhesive layer. Peeling strengths of these four kinds of sheets were measured under wet conditions. The results are shown in Table 12.
As shown in Table 12, the parchment paper laminates of Examples 7 and 8 prepared by using the modified block copolymer of this invention have an excellent peeling strength under wet conditions. In contrast to it, the parchment paper laminate of Comparative Example 7 prepared by using the block copolymer before modification and that of Comparative Example 8 prepared by using the ionomer resin are inferior in peeling strength under wet conditions, demonstrating that these resins have no sufficient adhesion to parchment paper.
As above, if the modified block copolymer of this invention is used as an adhesive layer, parchment paper can easily be bonded by the conventional bonding techniques such as wet lamination, dry lamination, hot melt lamination, extrusion lamination, hot press, etc. and there can be obtained a laminate containing a layer of parchment paper and having so sufficient an adhesion under wet conditions as has not been obtained hitherto.
TABLE 12 No.
Item Example 7 Example 8 Comparative Comparative Example 7 Example 8 Layer A Parchment Parchment Parchment Parchment paper paper paper paper Layer B Polymer Structure of (adhesive Sample A Sample B before lonomer laminate layer modifica polymer) tion of Sample A Layer C HDPE HDPE HDPE HDPE Peeling strength* 110 110 12 16 (girl25 mm) Peeling surface Layer awl Layer awl Layer N Layer A Layer B Layer B Layer B Layer B Note: * Peeling strength measured after dipping the sample in water for 60 minutes.

Claims (14)

1. A multi-layer laminate comprising at least one A-B double layer structure, in which layer A is a layer comprising at least one material selected from olefin polymers, polyamide polymers, saturated polyester polymers, acrylate polymers, polyether polymers, polycarbonate polymers, polyurethane polymers, acrylonitrile polymers, vinylidene chloride polymers, thermosetting resins, vulcanized rubbers, glass and papers, and layer B is a layer comprising mainly a modified block copolymer in which an unsaturated carboxylic acid or a derivative thereof is grafted on a styrene-butadiene block copolymer.
2. A laminate according to claim 1 wherein said styrene-butadiene block copolymer contains two or more polymer blocks composed mainly of butadiene.
3. A laminate according to claim 1 or 2, wherein the weight ratio of styrene to butadiene in said styrene-butadiene block copolymer is in the range of 10/90-90/10.
4. A laminate according to any one of claims 1 to 3, wherein the content of said unsaturated carboxylic acid or derivative thereof in the modified block copolymer is 0.05 - 5% by weight.
5. A laminate according to claim 4 wherein the content of said unsaturated carboxylic acid or derivative thereof in the modified block copolymer is 0.05 - 2% by weight.
6. A laminate according to claim 4 wherein the content of said unsaturated carboxylic acid or derivative thereof in the modified block copolymer is 0.05 - 1% by weight.
7. A laminate according to any one of claims 1 to 6 wherein said unsaturated carboxylic acid or derivative thereof is selected from maleic acid, fumaric acid and maleic anhydride.
8. A laminate according to any one of claims 1 to 7 wherein layer A is a gas barrier polymer and layer B comprises a styrene-butadiene copolymer having a styrene content of at least 65% by weight.
9. A laminate according to claim 8 wherein layer A comprises nylon 6, nylon 6,6, polyethylene terephthalate or ethylene-vinyl alcohol copolymer.
10. A laminate according to any one of claims 1 to 7 comprising an A-B-C triple layer structure wherein layer C is a layer comprising at least one material selected from olefin polymers, styrene polymers, polyamide polymers, thermoplastic polyester polymers, acrylate polymers, polyether polymers, polycarbonate polymers, acrylonitrile polymers, vinyl chloride polymers, vinylidene chloride polymers, thermosetting resins, vulcanised rubbers, glass, papers, metals, wood, woven and non-woven fabrics.
11. A laminate according to claim 10 wherein layer A is a gas barrier material and layer C is aluminum or a general purpose resin.
12. A laminate according to claim 11 wherein layer A comprises a polyamide polymer, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, polyacrylonitrile or polyvinylidene chloride, and layer C is aluminum or comprises polyethylene, polypropylene, polystyrene or high impact polystyrene.
13. A laminate according to claim 1 substantially as described in any one of the Examples.
14. A multi-layer laminate comprising at least one A-B double layer structure, in which layer A is a layer comprising at least one material selected from olefin polymers, polyamide polymers, saturated polyester polymers, acrylate polymers, polyether polymers, polycarbonate polymers, polyurethane polymers, acrylonitrile polymers, vinylidene chloride polymers, thermosetting resins, vulcanized rubbers, glass and papers, and layer B is a layer comprising at least 60% by weight of a modified block copolymer in which an unsaturated carboxylic acid or a derivative thereof is grafted on a styrene-butadiene block copolymer to improve the adhesion characteristic of the block copolymer, the balance of the layer being conventional additives and/or other polymers which do not significantly affect the adhesion of the modified block copolymer, the styrene block of the block copolymer optionally containing a minor amount of butadiene, the butadiene block of the block copolymer optionally containing a minor amount of styrene, and a minor portion of the styrene content of the block copolymer optionally being replaced by one or more vinyl or vinylidene aromatic hydrocarbons.
GB7944020A 1978-12-27 1979-12-21 Laminate with inerlaminate adhesion Expired GB2040223B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP16002178A JPS5587551A (en) 1978-12-27 1978-12-27 Original laminated piece
JP3221579A JPS55125175A (en) 1979-03-22 1979-03-22 Bonding of acrylonitrile resin
JP8010479A JPS564797A (en) 1979-06-27 1979-06-27 Adhering of parchment paper

Publications (2)

Publication Number Publication Date
GB2040223A true GB2040223A (en) 1980-08-28
GB2040223B GB2040223B (en) 1983-05-25

Family

ID=27287622

Family Applications (1)

Application Number Title Priority Date Filing Date
GB7944020A Expired GB2040223B (en) 1978-12-27 1979-12-21 Laminate with inerlaminate adhesion

Country Status (3)

Country Link
DE (1) DE2952359C2 (en)
FR (1) FR2445223A1 (en)
GB (1) GB2040223B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0083157A2 (en) * 1981-12-28 1983-07-06 Mobil Oil Corporation Flexible film laminates
EP0399594A1 (en) * 1989-05-24 1990-11-28 SOLVAY (Société Anonyme) Laminate assembly
US5549943A (en) * 1992-09-23 1996-08-27 Viskase Corporation Heat shrinkable nylon food casing with a polyolefin core layer
AU678491B2 (en) * 1993-06-28 1997-05-29 Elf Atochem S.A. Composite structure comprising an elastomer and a thermoplastic polymer, method of preparation and object containing said structure
US5698279A (en) * 1992-09-23 1997-12-16 Viskase Corporation Heat shrinkable nylon food casing having a functionalized ethylenic polymer core layer
EP0857758A1 (en) * 1997-02-10 1998-08-12 Mitsubishi Chemical Corporation Adhesive resin compositions, laminates, production method thereof and oriented films
EP1384572A1 (en) * 2002-07-22 2004-01-28 Cristales Curvados, S.A. (Cricursa) Opaque multilayered decorative plate
US8962113B2 (en) 2004-06-03 2015-02-24 Mitsubishi Plastics, Inc. Heat-shrinkable laminate film, molded product and heat shrinkable label employing the film, and container
WO2020083902A1 (en) * 2018-10-26 2020-04-30 Abu Dhabi Polymers Co. Ltd (Borouge) L.L.C. Multi-layered article with improved adhesion

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986004858A1 (en) * 1985-02-18 1986-08-28 Ashimori Kogyo Kabushiki Kaisha Lining material for duct
NL8602159A (en) * 1986-08-26 1988-03-16 Gen Electric STRUCTURE OF POLYALKYLENE PHTHALATE LAYER AND POLYSTYRENE LAYER.
JPS63145026A (en) * 1986-12-10 1988-06-17 三菱油化株式会社 Thermoplastic halogen-contained resin laminate
US5104733A (en) * 1990-02-23 1992-04-14 Shell Oil Company Adhesive for adhering polybutylene to metal
FR2662638B1 (en) * 1990-05-31 1997-09-05 Nok Corp COLD RESISTANT LAMINATED SHEET GAS BARRIER, BLADDER FOR ACCUMULATOR AND ACCUMULATOR COMPRISING SAME.
DE4214192A1 (en) * 1992-04-30 1993-11-11 Bayer Ag Composite molded body
FR2702183B1 (en) * 1993-03-05 1995-08-04 France Assessoires Automobiles ADHESIVE FIXING FLOOR MAT.
FR2708533B1 (en) * 1993-07-30 1995-10-20 France Assessoires Automobiles Floor mats with adhesion fixing.
DE10007884B4 (en) * 2000-02-21 2004-08-12 Benecke-Kaliko Ag Compressible and vacuum-formable, grained composite film, process for its production and its use
KR20080080543A (en) * 2005-12-14 2008-09-04 가부시키가이샤 구라레 Block copolymer and hydrogenated product thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242038A (en) * 1964-08-11 1966-03-22 Shell Oil Co Laminates of polyalkenes and certain block copolymers
FR1481828A (en) * 1965-06-14 1967-08-21
BE690580A (en) * 1966-12-02 1967-05-16
US3438845A (en) * 1967-11-20 1969-04-15 Monsanto Co Laminates of styrene polymers and block copolymers
GB1264955A (en) * 1968-06-24 1972-02-23
US3959568A (en) * 1972-09-19 1976-05-25 Phillips Petroleum Company α-Alkoxystyrene resinous adhesives and laminates
JPS5526611B2 (en) * 1973-05-09 1980-07-15
US4007311A (en) * 1975-11-06 1977-02-08 Shell Oil Company Polyacrylate-grafted block copolymer adhesive compositions

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0083157A3 (en) * 1981-12-28 1984-06-13 Mobil Oil Corporation Flexible film laminates
EP0083157A2 (en) * 1981-12-28 1983-07-06 Mobil Oil Corporation Flexible film laminates
EP0399594A1 (en) * 1989-05-24 1990-11-28 SOLVAY (Société Anonyme) Laminate assembly
FR2647391A1 (en) * 1989-05-24 1990-11-30 Solvay LAMINATE COMPLEX CONSISTING OF A CARRIER SHEET COATED WITH A FILM COMPRISING AT LEAST ONE LAYER OF A SEMI-AROMATIC POLYAMIDE AND METHOD FOR OBTAINING SAME
US5164267A (en) * 1989-05-24 1992-11-17 Solvay & Cie (Societe Anonyme) Laminated composite
US5698279A (en) * 1992-09-23 1997-12-16 Viskase Corporation Heat shrinkable nylon food casing having a functionalized ethylenic polymer core layer
US5549943A (en) * 1992-09-23 1996-08-27 Viskase Corporation Heat shrinkable nylon food casing with a polyolefin core layer
AU678491B2 (en) * 1993-06-28 1997-05-29 Elf Atochem S.A. Composite structure comprising an elastomer and a thermoplastic polymer, method of preparation and object containing said structure
EP0857758A1 (en) * 1997-02-10 1998-08-12 Mitsubishi Chemical Corporation Adhesive resin compositions, laminates, production method thereof and oriented films
US6214476B1 (en) 1997-02-10 2001-04-10 Mitsubishi Chemical Corporation Adhesive resin compositions, laminates, production method thereof and oriented films
EP1384572A1 (en) * 2002-07-22 2004-01-28 Cristales Curvados, S.A. (Cricursa) Opaque multilayered decorative plate
US8962113B2 (en) 2004-06-03 2015-02-24 Mitsubishi Plastics, Inc. Heat-shrinkable laminate film, molded product and heat shrinkable label employing the film, and container
WO2020083902A1 (en) * 2018-10-26 2020-04-30 Abu Dhabi Polymers Co. Ltd (Borouge) L.L.C. Multi-layered article with improved adhesion
CN112930260A (en) * 2018-10-26 2021-06-08 阿布扎比聚合物有限公司(博禄) Multi-layer articles with improved adhesion

Also Published As

Publication number Publication date
GB2040223B (en) 1983-05-25
FR2445223B1 (en) 1983-12-30
DE2952359A1 (en) 1980-07-03
FR2445223A1 (en) 1980-07-25
DE2952359C2 (en) 1984-03-15

Similar Documents

Publication Publication Date Title
US4332858A (en) Multi-layer laminate comprising a modified styrene-butadiene block copolymer
GB2040223A (en) Laminate with improved inter- laminate adhesion
AU2004235628B2 (en) Oxygen absorption resin composition
EP1912789A1 (en) Flexible packaging laminate films including a block copolymer layer
CA1311999C (en) Laminated structure
CN105121162A (en) Tie-layer adhesives for styrenic multi-layer structures
JP2010500450A (en) Adhesive composition
US6184289B1 (en) Styrene resin composition and molding thereof
US4898784A (en) Tie layer composition and laminated structures containing same
JPS6331385B2 (en)
JPH01115978A (en) Adhesive
JP4945866B2 (en) Ethylene-based resin composition for extrusion lamination, laminate using the same, and method for producing laminate
EP0695326B1 (en) Heat-sealable polystyrene-based blends
US20040126524A1 (en) Gas-barrier thermoplastic film and substrate/film composite material
JPS6221037B2 (en)
JPS621430B2 (en)
JPS6324021B2 (en)
JPH0258104B2 (en)
EP0483736A2 (en) Resin composition
JPS63264688A (en) Adhesive
JPS631343B2 (en)
JP3265727B2 (en) Laminate
JPS6324830B2 (en)
JPS6213911B2 (en)
JPS6213910B2 (en)

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19981221