JPS6213910B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel laminate, and more particularly to a laminate with improved interlayer adhesion. Conventionally, different types of materials have been bonded together to form a laminate, which gives the advantages of both materials, and the same material is sandwiched between different types of materials to create a laminate, which eliminates the disadvantages of the outer layer material. Many attempts have been made to produce various laminates that compensate for this. Materials for such laminates include metal foils such as aluminum foil and copper foil, paper, cellophane, etc.
Various thermoplastic resins include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyethylene terephthalate, nylon,
Polycarbonate, polystyrene, high-impact polystyrene, polyvinylidene chloride, ABS resin, etc. are used. These laminates are used in the form of sheets, films, blow molded products, and the like. These laminates are generally produced by bonding sheets or films of the same or different materials using an adhesive, or by coextrusion without using an adhesive. However, depending on the type of materials to be laminated or their combination, a sufficient adhesive effect may not be obtained. Especially when obtaining a laminate by a coextrusion method that does not use an adhesive, mutual adhesiveness may not be obtained. It is not possible to use materials that do not exist. Therefore, when obtaining a laminate of mutually non-adhesive materials using a coextrusion method, a method is used in which a material that is adhesive to both materials is used as an adhesive layer, such as ethylene-vinyl acetate copolymer. , ionomer resin,
Styrene-butadiene block copolymers and the like are used. However, these resins also have problems, such as not necessarily providing a sufficient adhesive effect depending on the type of material to be coextruded, and poor durability of adhesive strength, poor water resistance, etc. The present inventors have already discovered that a modified block copolymer obtained by bonding a molecular unit containing an unsaturated dicarboxylic acid group or its derivative group to a vinyl aromatic compound-conjugated diene compound block copolymer can be used with various materials. As a result of further intensive studies, we found that compositions consisting of the above-mentioned modified block copolymer and other polar thermoplastic polymers have been found to have excellent adhesion and are suitable as materials for laminates. The inventors have discovered that this material has good adhesion to other materials and is suitable for use as a material for laminates, allowing combinations of a wide variety of materials, and has thus arrived at the present invention. The gist of the present invention is a multilayer laminate of two or more layers containing an AB two-layer structure, wherein the A layer and the B layer are as follows. A layer: polyolefin polymer, polystyrene polymer, polyamide polymer, polyester polymer, polyacrylate polymer, polyether polymer, polyacrylonitrile polymer, polyurethane polymer, polycarbonate polymer , a layer containing at least one selected from polyvinyl chloride polymer, polyvinylidene chloride polymer, polyvinyl alcohol polymer, thermosetting resin, vulcanized rubber, glass, metal, and paper; layer B; : (i) a modified block copolymer in which a molecular unit containing a dicarboxylic acid group or its derivative group is bonded to a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound; and (ii) a polyamide-based polymer polyester. At least one type of polar heat selected from polyvinyl chloride polymers, polyacrylate polymers, polyether polymers, polyurethane polymers, polycarbonate polymers, polyvinyl chloride polymers, and polyvinyl alcohol polymers. A layer consisting of a thermoplastic polymer composition consisting of a plastic polymer. The A layer of the present invention is a material that has good adhesion to the thermoplastic polymer composition of the B layer, which will be described later, and as described above, these materials include polyolefin polymers,
Polystyrene polymers, polyamide polymers, polyester polymers, polyacrylate polymers, polyether polymers, polyacrylonitrile polymers, polyurethane polymers, polycarbonate polymers, polyvinyl chloride polymers, The material contains at least one selected from polyvinylidene chloride polymers, polyvinyl alcohol polymers, thermosetting resins, vulcanized rubber, glass, metals, and paper. The A layer of the present invention may be a composition as well as a single substance. The polyolefin polymer referred to in the present invention is
Ethylene, propylene, 1-butene, 2-butene
Polymers of olefinic monomers such as iso-butene and 1,3-butadiene, copolymers of two or more different olefinic monomers, and copolymers of olefinic monomers and other monomers. It is a combination and a modified product thereof. Examples of polymers of these olefinic monomers include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene,
Examples of copolymers include ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Examples of these modified products include ionomers (ionically crosslinked products of ethylene-methacrylic acid copolymers), chlorosulfonated polyethylene, and chlorinated polyethylene. The styrenic polymer referred to in the present invention refers to polystyrene or a copolymer of a major amount of styrene and other monomers, and those modified with a rubber component. Polystyrene, high impact polystyrene, acrylonitrile
Styrene copolymer, styrene-maleic anhydride copolymer, methylstyrene methacrylate copolymer,
Examples include ABS resin and MBS resin. The polyamide polymer referred to in the present invention is a polycondensate of diamide and dicarboxylic acid, a polycondensate of aminocarboxylic acid, and a ring-opening polymer of cyclic lactam.
Examples of these polyamide-based polymers include nylon-6, nylon-6.6, nylon-11, nylon-12, nylon-6-nylon-6.6 copolymers, and aliphatic amine and dimer copolymers. Examples include polyamide made of acid. The polyester polymers used in the present invention are polycondensates of dicarboxylic acids and diols, and ring-opening polymers of cyclic lactones, examples of which include polyethylene terephthalate, polybutylene terephthalate, polycaprolactane, and copolymerized polyesters. Examples include. The polyacrylate polymer referred to in the present invention is
It is a polymer or copolymer containing acrylic ester or methacrylic ester as a monomer, and examples thereof include polymethyl methacrylate and polybutyl methacrylate. The polyacrylonitrile polymer referred to in the present invention is a polymer of acrylonitrile or methacrylonitrile, or a copolymer mainly composed of these and other monomers. Examples thereof include acrylonitrile-methyl acrylate copolymer. Examples include polymers and polyacrylonitrile. The polyether polymer referred to in the present invention is a polymer having an ether bond in the molecule, and examples thereof include polyacetal, polyethylene oxide, polypropylene oxide, polyphenylene ether, and the like. The polycarbonate polymer referred to in the present invention is
A typical example is a polymer obtained by reacting bisphenol A with phosgene or diphenyl carbonate. The polyurethane polymer referred to in the present invention is a polymer having a urethane bond in the molecule, and is obtained by polyaddition of a diisocyanate component and a diol component. Thermoplastic polyurethane is a preferable material, and urethane foam etc. It can be used for layer A of the present invention. The polyvinyl chloride polymer referred to in the present invention is a homopolymer of vinyl chloride or a copolymer of vinyl chloride and other monomers, examples of which include vinyl chloride-vinyl acetate copolymer. It is representative. In addition, soft materials containing plasticizers and the like also fall within this range. Moreover, the polyvinylidene chloride-based polymer is a homopolymer of vinylidene chloride or a copolymer with other monomers. The polyvinyl alcohol polymer used in the present invention is usually obtained by saponifying a polymer of vinyl ester such as vinyl acetate or a copolymer with other monomers. Examples include alcohol, ethylene-vinyl alcohol copolymer, and the like. Thermosetting resins in the present invention include unsaturated polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, alkyd resins, furan resins, ketone resins, benzoguanamine resins, and the like. The vulcanized rubber referred to in the present invention refers to 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. . In the present invention, paper refers to materials commonly called paper, as well as cellophane and parchment paper (sulfuric acid paper).
including. The metals used in the present invention include iron, aluminum,
Copper, brass, tin, zinc, and alloys containing them are used in the laminate of the present invention in the form of plates or foils. Further, the glass referred to in the present invention includes various kinds of hard and soft glasses. Next, layer B of the present invention is (i) a modified block copolymer formed by bonding a molecular unit containing a dicarboxylic acid group or a derivative group thereof to a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound. and (ii) among polyamide-based polymers, polyester-based polymers, polyacrylate-based polymers, polyether-based polymers, polyurethane-based polymers, polycarbonate-based polymers, polyvinyl chloride-based polymers, and polyvinyl alcohol-based polymers. This layer is made of a thermoplastic polymer composition including at least one polar thermoplastic polymer selected from the following. The modified block copolymer of component (i) forming layer B is a polymer formed by bonding a dicarboxylic acid group or a derivative group thereof to a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound as a base. It is a combination. The block copolymer serving as the base is typically obtained by an anionic polymerization method using a lithium compound as a catalyst, and the content of the vinyl aromatic compound is generally 5 to 95% by weight, preferably 15-85% by weight. and contains one or more, preferably two or more, polymer blocks (A) mainly composed of a vinyl aromatic compound, and one or more polymer blocks (B) mainly composed of a conjugated diene compound,
The weight ratio of each polymer block is preferably A/B in the range of 10/90 to 90/10. Among these, when the content of the vinyl aromatic compound is 70% by weight or less, preferably 50% by weight or less, the block copolymer is rubber-like, and when it exceeds 70% by weight, the block copolymer is resin-like. This state is maintained even after degeneration. Furthermore, the specific properties of the composition of layer B used in the laminate of the present invention, such as hardness, vary depending on the content of the vinyl aromatic compound in the block copolymer. The content of the vinyl aromatic compound in block A of the block copolymer is 60% by weight or more, preferably 80% by weight or more, particularly preferably 100% by weight.
On the other hand, the content of vinyl aromatic compounds in block B is 40% by weight or less, preferably 30% by weight or less. In each block, if a minor component is present, its distribution may be random, tapered, partially block-like, or any combination thereof. When there are two or more polymer blocks, they may have the same structure or different structures. Vinyl aromatic compounds constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene, etc., and conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, etc. As the block copolymer of the present invention, a styrene-butadiene block copolymer is preferred. The number average molecular weight of block A or B is 1000~
300000, preferably in the range of 5000-100000,
The number average molecular weight of the entire block copolymer is 10,000.
-500000, preferably 20000-300000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is 1.01-10. Further, the molecular structure of the block copolymer may be linear, branched, radial obtained by using a polyfunctional coupling agent, or any combination thereof. The above-mentioned limitations on the polymer structure of the block copolymer are necessary for the modified block copolymer to achieve the effects of the present invention. It is possible to combine two or more types of block copolymers with different structures. Next, the modified block copolymer of the present invention is obtained by adding an unsaturated dicarboxylic acid or a derivative thereof to the above block copolymer, and these unsaturated dicarboxylic acids or derivatives thereof are , at the position of its active unsaturated bond,
It is added to the conjugated diene moiety of the block copolymer. In forming the composition of layer B, these should be bonded in an average of one or more to each molecule of the block copolymer, and should be present in an amount of 0.05 to 20 parts by weight per 100 parts by weight of the block copolymer. This is necessary in terms of compatibility with component (ii) and the adhesion of layer A in the case of forming a laminate. If the above amount is less than 0.05 parts by weight, the improvement effect will not be very noticeable, and even if it exceeds 20 parts by weight, the effect will be slight compared to less than 20 parts by weight. Further, it is preferable that the above amount is 10 parts by weight or less from the viewpoint of processability of the composition of layer B, and furthermore, it is preferable that the above amount is 5 parts by weight or less so that moisture in the air can be absorbed by the modified block copolymer of the composition. This is preferable in order to prevent foaming during melt processing due to absorption by the combined components. Examples of the unsaturated dicarboxylic acids or derivatives thereof include maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-
These include 1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, and acid anhydrides, esters, amides, and imides of these dicarboxylic acids. Particularly preferred are maleic acid, fumaric acid and maleic anhydride. A modified block copolymer is a block copolymer and an unsaturated dicarboxylic acid or a derivative thereof.
It is obtained by reaction in the melt or in the solution state, with or without the use of a radical initiator. The method for producing these modified block copolymers is not particularly limited in the present invention; A manufacturing method that results in poor performance is not preferred. For example, as shown in Japanese Patent Application No. 53-99102 related to the applicant's earlier application, an addition reaction is carried out in an extruder or the like in the presence of a radical inhibitor under melt mixing conditions that do not substantially generate radicals. A method of carrying out is preferred. Furthermore, the modified block copolymer may be ionicly crosslinked with mono-, di- or trivalent metal ions. This ionic crosslinked product is obtained by crosslinking the above-mentioned modified block copolymer with one or a mixture of two or more of monovalent, divalent, and trivalent metal ions through ionic bonds. It is obtained by reacting a modified block copolymer with any one or a mixture of two or more of monovalent, divalent, and trivalent metal compounds as a crosslinking agent compound. In the above ionic crosslinked product, the dicarboxylic acid group or its derivative group of the modified block copolymer is
Ionization is achieved by adding a crosslinker compound. The amount of ionization can be adjusted by adjusting the amount of the crosslinking agent compound added, and the amount is measured using, for example, an infrared spectrophotometer. The amount of the crosslinking agent compound to be added is such that a portion or all of the dicarboxylic acid groups or derivative groups thereof contained in the modified block copolymer are ionized, and the ionization reaction described above proceeds almost quantitatively. In order to obtain the desired amount of ionization, an excess of the crosslinking agent over the theoretical amount may be necessary. In order to effectively obtain an ionic crosslinked product, it is preferable that the molar ratio between the metal compound and the dicarboxylic acid group or its derivative group contained in the modified block copolymer is 0.1 to 3.0. The crosslinking agent compound used to obtain the ionic crosslinked product by adding it to the modified block copolymer may be any one of the metal compounds of Groups 1, 2, and 3 of the periodic table; A mixture of two or more types is preferred, and specific examples thereof include sodium compounds, potassium compounds, magnesium compounds, calcium compounds, zinc compounds, and aluminum compounds. Preferred examples of these metal compounds are hydroxides, alcoholates, and carboxylates. A specific method for obtaining an ionic crosslinked product of a modified block copolymer is to add a crosslinking agent compound to a molten modified block copolymer, or to dissolve the modified block copolymer in an appropriate solvent. Examples include a method in which a crosslinking agent compound is added to this solution to cause a crosslinking reaction, and a method in which a modified block copolymer is used as a latex and a crosslinking agent is added thereto. It can be used as a method to obtain a crosslinked product. Next, the polar thermoplastic polymer that is component (ii) of layer B is a polyamide polymer, a polyester polymer, a polyacrylate polymer, a polyether polymer, a polyurethane polymer, or a polycarbonate polymer. The polymer is selected from among polymers, polyvinyl chloride polymers, and polyvinyl alcohol polymers. These thermoplastic polymers are as described above with respect to the A layer. These polymers used as the composition of layer B have good compatibility with the modified block copolymer, which is another component of layer B. In addition, for layer B, polymers called oligomers that have a lower molecular weight than those used in ordinary molding materials can also be used as the thermoplastic polymer of component (ii), and have fluidity. , is often preferable in terms of adhesiveness, etc. Component (i) of the thermoplastic polymer composition forming layer B
Although the composition ratio of component (ii) and component (ii) can be set arbitrarily depending on the purpose of use, one of the features of the present invention is that As a result, the adhesive performance of the thermoplastic polymer of component (ii) may be improved, and it can be used in laminates without significantly impairing the properties of component (ii). In addition, when there is a large amount of component (i), for a specific material,
It may exhibit better adhesion than component (i) alone. In particular, when the A layer of the laminate is a polar thermoplastic polymer, when the component (ii) of the B layer is the same as that of the A layer, the adhesion between the A layer/B layer is improved;
The composition of the layer also retains sufficient adhesion to other materials. In addition, when components (i) and (ii) have close composition ratios, the phases of both are interwoven with each other.
It takes on a so-called mesh-like form and has the effect of improving adhesion to various materials. Mixing of components (i) and (ii) of the composition of layer B can be carried out using various known mixers, but mixing in a hot molten state using an extruder, Banbury mixer, mixing roll, etc. A preferred method is a method in which both components are mixed by dissolving them in a suitable solvent. Moreover, such mixing may be performed in advance, or may be performed at the stage of processing into a laminate as described later. Incidentally, various additives conventionally used in the field of plastics or rubber can be added to the composition of the B layer insofar as they do not deteriorate the properties of the B layer. These additives include stabilizers, UV inhibitors, inorganic or organic fillers,
Examples include coloring agents. The laminate of the present invention is a multilayer laminate of two or more layers comprising a two-layer structure of A-B, and in the case of a multilayer laminate of three or more layers, other layers are bonded to layer A or layer B. It must be made of possible materials. In particular, layer B has good adhesion to various materials and is useful as an adhesive layer when combined with other materials to form a three-layer laminate of ABC. The material used for the C layer that can be bonded to the B layer is the above-mentioned A
In addition to the materials used for the layer, various known materials may be used, such as wood, woven fabric, nonwoven fabric, ceramic material, etc. As mentioned above, the modified block copolymer used for the B layer has good adhesion to a large number of materials, so by using the B layer as an adhesive layer, it is difficult to obtain a copolymer that is difficult to obtain in the past. Another feature of the present invention is that it is possible to obtain multilayer laminates with various combinations. For example, in the present invention, the A layer is made of a so-called gas barrier material such as a polyamide polymer such as nylon-6 or nylon-6/6, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, polyacrylonitrile, or polyvinylidene chloride. The B layer is used as an adhesive layer, and the C layer is made of aluminum, polyethylene, polypropylene, polystyrene, or a general-purpose resin such as high-impact polystyrene, which has gas barrier properties, water vapor barrier properties, and mechanical strength. It is possible to obtain a three-layer laminate with excellent adhesion between the layers. Laminates made by combining these gas barrier materials with general-purpose resins or aluminum do not always have sufficient interlayer adhesion when conventional adhesives or adhesive polymers are used.
Although this was a practical problem, compositions containing the modified block copolymers of the present invention had excellent adhesion to both and yielded useful laminates. Furthermore, in the present invention, the thermoplastic polymer composition of layer B is polyethylene terephthalate, ethylene-vinyl alcohol, nylon-6, nylon-
6.6, etc., the characteristics of these polymers can be maintained, so as layer A,
It is also possible to use the common resins polyethylene, polypropylene, polystyrene, high-impact polystyrene, and aluminum to create a useful two-layer laminate. Furthermore, the modified block copolymer of component (i) of the thermoplastic polymer composition of layer B is resinous if the vinyl aromatic compound content in the base block copolymer exceeds 70% by weight. , and when the B layer is mainly composed of a modified block copolymer, the B layer retains sufficient mechanical properties. Such a composition is used as the B layer, and a gas barrier material such as nylon-6, nylon-6.6, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, polyacrylonitrile polymer, etc. is used as the A layer. Even so, it is possible to obtain a two-layer A-B laminate having gas barrier properties and sufficient mechanical strength. The laminate of the present invention can be manufactured by any conventionally commonly used method. Such methods include an extrusion lamination method in which the composition used for the B layer is made into a heated molten film using an extruder and is pressed onto the adherend; the composition used for the B layer and the adherend are separated into A coextrusion method in which the composition is heated and melted using an extruder and bonded in a multilayer die; A method in which the composition is layered on the adherend in the form of a sheet or film in advance and bonded under heat using a hot press; There is a hot lamination method in which the adhesive is applied to a film-formed adherend using an extrusion method or a casting method; other methods include a method in which the material is dissolved in a solvent; and a method in which it is made into latex. The composition of the present invention is preferably laminated by hot melt bonding methods such as extrusion lamination, coextrusion, and pressing. In addition, in the above method, when using an extruder, the composition used for the B layer can be dry blended in the form of pellets, powder, etc., and melted and mixed in the extruder to form a laminate. The process is not particularly complicated compared to conventional coextrusion methods. The material forming the laminate of the present invention can also be surface-treated to improve adhesion. The amount of the B layer composition used in the laminate may be such that the laminate has sufficient adhesive performance. When imparting special functions such as oil resistance, gas barrier properties, rigidity, impact resistance, and flexibility, a sufficient amount is required to fully exhibit the functions. The laminate obtained by the method of the present invention includes a film,
It can be widely used in the form of a packaging film in the form of a sheet, and as a molding material for vacuum forming and pressure forming of multilayer hollow products by coextrusion. Some Examples are shown below, but these are for explaining the present invention more specifically, and it goes without saying that the scope of the present invention is not limited thereto. Reference Example [Preparation of Modified Block Copolymer] A modified block copolymer (Sample P) in which maleic anhydride was grafted by the method shown below using Sample P, which is a thermoplastic elastomer of styrene-butadiene block copolymer. I got it. Note that sample p was obtained in a hexane solution using n-butyllithium as a polymerization catalyst,
Based on the polymerization method and analysis results, it is thought to have the following structure. Polymer structure: B ₁ −S ₁ −B ₂ −S ₂ (linear) B ₁ = 18% by weight, [B] / [S] = 16/2 (tapered) S ₁ = 17% by weight, [B] / [S] = 0/17 B ₂ = 49% by weight, [B] / [S] = 46/3 (tapered) S ₂ = 16% by weight, [B] / [S] = 0/16 However, B _o ... Polymer block mainly composed of butadiene S _o ... Polymer block mainly composed of styrene The integer n represents the order along the molecular chain [B] ... Butadiene content (weight relative to the entire block copolymer) %) Similar notations will be used in the following examples. Styrene content: 38% by weight Block styrene content: 33% by weight Weight average molecular weight (Mw): 81000 Number average molecular weight (Mn): 62000 Melt index: 11.0g/10min (JIS-K
-6870, load 5Kg, 200℃) 2.5 parts by weight of maleic anhydride and 0.3 parts by weight of BHT as anti-gelling agent for 100 parts by weight of sample p.
(butyl hydroxytoluene) and 0.2 parts by weight of phenothiazine were added, and these were mixed uniformly using a mixer. This mixture was supplied to a 40 mm extruder (single screw, full-flight screw, L/D=24) under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 190 to 210°C. The obtained polymer was dried under reduced pressure to remove unreacted maleic anhydride. The analysis results of the modified block copolymer (sample P) are as follows:
The index was 6.8 g/10 min, the toluene insoluble content was 0.05% by weight, and the amount of maleic anhydride added was 0.96 parts by weight per 100 parts by weight of the block copolymer, as determined by titration with sodium methylate. In addition, Solprene-T414, a commercially available styrene-butadiene block copolymer (Melt Index, manufactured by Nippon Elastomer Co., Ltd., 5.3 g/
min, styrene content 40% by weight) (sample q) and sample r, a prototype styrene-butadiene block with styrene/butadiene/styrene = 40/20/40 and a melt index of 4.8 g/10 min. Sample Q and Sample R, which are modified block copolymers to which maleic anhydride was added, were obtained by using a polymer and an extruder similar to that used to obtain Sample P. Table 1 shows the characteristic values of these samples.
Shown below.

[Table] Examples 1 and 2 and Comparative Example 1 In order to test the adhesion between various materials and the composition of layer B used in the laminate of the present invention, samples P, Q, and R of modified block copolymers were used. and sample p of unmodified block copolymer were used as component (i) of layer B, and various materials shown in Table 2 were used as components of layer A or B.
It was used as (ii). The compositions used for layer B were mixed using a Brabender plastograph at a temperature and time appropriate for each composition, and then compression molded (conditions such as temperature and pressure were changed as appropriate for each). , 0.3 to 0.5 m sheets were used in the adhesion test. As the material for layer A, commercially available plates, sheets, and films were used as they were, or compression-molded sheets were used. A heat press is used to press the A layer and B layer together, and the temperature is
Suitable conditions for component (ii) of layer A or layer B were selected from the range of 160 to 260° C. and pressure of 10 to 50 kg/cm ² . In the case of glass, it was crimped with a weight (10 kg) in an oven. Tables 3 and 4 show each material when a composition of a modified block copolymer and polyurethane was used as the B layer, and when a composition using an unmodified block copolymer was used as a comparative example. The results of adhesion with Table 5 also shows the results when a modified block copolymer and a copolymerized polyester (1,4-butanediol was used as the diol and terephthalic acid, isophthalic acid, and adipic acid were used as the dicarboxylic acid) were used as the B layer. The results of adhesion with each material are shown. As is clear from the adhesiveness evaluation results in Tables 3 to 5, the composition used for layer B in the laminate of the present invention has excellent adhesiveness to the various materials of layer A.

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[Table] Example 3 Adhesion tests were conducted using four types of materials for layer A and various types of component (ii) of the composition for layer B.
The results are shown in Table 6. As is clear from the results in Table 6, all exhibit good adhesion. Example 4 The peel strength of a laminate using the same polymer or the same type of polymer as component (ii) of layer A and layer B was measured, and the results are shown in Table 7. In addition, numbers 4-8, 4-9 and 4- of Example 4
In Example No. 10, a polymer (sample S) obtained by ionic crosslinking by adding 0.5 mol of sodium methylate per acid anhydride group to sample P was used as component (i) of layer B. As is clear from the results in Table 7, all of them have excellent adhesive strength, and the composition of layer B in Table 7 has peel strength that is not a problem for HIPS as a laminate. have.

【table】

[Table] Example 5 and Comparative Example 2 Using two or three 25 mm extruders and a die for coextrusion sheets, laminate sheets for adhesion testing of two or three layers shown in Table 8 were prepared. Created. The composition used for layer B was previously mixed and pelletized. The results are shown in Table 8. As shown in Table 8, the laminates of Examples 5-1 to 5-3 in which the modified block copolymer-containing composition of the present invention obtained by the coextrusion method was used as the B layer were the same as those of Comparative Examples 2-1 to 5-3.
Compared to the laminate in which layer B was made of a composition containing the unmodified block copolymer No. 2-3, the adhesive strength between the layers was excellent, demonstrating the usefulness of the laminate of the present invention.

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Claims (1)

[Scope of Claims] 1. A multilayer laminate of two or more layers containing an A-B two-layer structure, characterized in that the A layer and the B layer are as follows. A layer: polyolefin polymer, polystyrene polymer, polyamide polymer, polyester polymer, polyacrylate polymer, polyether polymer, polyacrylonitrile polymer, polyurethane polymer, polycarbonate polymer A layer containing at least one selected from polyvinyl chloride polymer, polyvinylidene chloride polymer, polyvinyl alcohol polymer, thermosetting resin, vulcanized rubber, glass, metal, and paper, layer B: ( i) a modified block copolymer formed by bonding a molecular unit containing a dicarboxylic acid group or its derivative group to a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound; (ii) a polyamide-based polymer; Polyester polymers, polyacrylate polymers, polyether polymers,
A layer comprising a thermoplastic polymer composition comprising at least one polar thermoplastic polymer selected from a polyurethane polymer, a polycarbonate polymer, a polyvinyl chloride polymer, and a polyvinyl alcohol polymer. 2 The modified block copolymer of component (i) of layer B contains 0.05 to 10 molecular units containing a dicarboxylic acid group or its derivative group per 100 parts by weight of the block copolymer.
The laminate according to claim 1, wherein the laminate contains parts by weight. 3. The laminate according to claim 2, wherein the dicarboxylic acid derivative group of component (i) of layer B is a dicarboxylic acid anhydride group. 4. A block copolymer comprising a vinyl aromatic compound and a conjugated diene compound as component (i) of layer B, wherein the content of the vinyl aromatic compound in the block copolymer is 5 to 70% by weight. laminate. 5. Claim No. 5, wherein the content of the vinyl aromatic compound in the block copolymer consisting of the vinyl aromatic compound and the conjugated diene compound as component (i) of layer B is more than 70% by weight and not more than 95% by weight. The laminate according to item 1. 6 The material of layer A contains a polar thermoplastic polymer, and the polar thermoplastic polymer of component (ii) of layer B is
The laminate according to claim 1, which is the same as that contained in the layers. 7 The modified block copolymer of component (i) of layer B is ionicly crosslinked with monovalent, divalent or trivalent metal ions using the dicarboxylic acid group or its derivative group as the crosslinking site. A laminate according to any one of claims 1 to 6.