JPH0258104B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a laminate having an adhesive layer made of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene having excellent peeling resistance, and particularly to a laminate produced by a hot-melt bonding method. [Prior Art] Traditionally, different materials have been bonded together to form a laminate to improve the properties of each material, such as strength, rigidity, hardness, colorability, printability, gas permeability,
Many attempts have been made to develop additive properties such as weather resistance and chemical resistance. Materials for such laminates include metal foils such as aluminum foil and copper foil;
In addition to paper and cellophane, various thermoplastic resins,
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. There is. These laminates are in the form of sheets, films,
Or it is used as a hollow molded product. 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. For example, in Japanese Patent Publication No. 52-22027,
A method is described in which a styrene-butadiene block copolymer is used as a binder when two different resins are coextruded. Mata Tokko Show 56
Publication No. 3183 describes a method in which a styrene-butadiene copolymer is used as an adhesive between a styrene resin sheet or film and a copolymer film mainly composed of vinylidene chloride.
Further, JP-A-55-126449 discloses a film in which a polypropylene sheet and a styrene resin sheet are laminated via a block copolymer of conjugated diene and styrene. However, the current situation is that conventional block copolymers do not yet provide satisfactory adhesive strength depending on the type of material to be coextruded. [Problems to be Solved by the Invention] The present invention aims to develop an adhesive that has excellent adhesive strength and good workability during coextrusion processing for laminated products made of different materials, especially coextruded laminate products. This was done with the aim of obtaining a laminate product with excellent peeling resistance. [Means and effects for solving the problems] The present invention provides a polymer block mainly composed of a conjugated diene at one end of a block copolymer molecular chain, and at the same time a polymer block mainly composed of a conjugated diene. The above conventional problems are solved by limiting the content of the vinyl aromatic hydrocarbon polymer block, the content of the vinyl aromatic hydrocarbon in the block copolymer, and the melt flow to specific ranges. This was done based on what was discovered. That is, the present invention provides a laminate made of two or more different materials, in which at least one layer of an acrylonitrile resin containing 50% by weight or more of an acrylonitrile monomer is used as the material of the laminate, and the acrylonitrile resin The general formula B-A-(B'-A') _o (In the above formula, A and A' are vinyl aromatic hydrocarbons The polymer blocks B and B' are polymer blocks mainly composed of conjugated dienes. n is an integer from 1 to 3.) The content of polymer block B in the molecular chain of the block copolymer is is 3 to 50% by weight, and the content of block A in the block B-A part is 25 to 50% by weight.
85% by weight, the weight ratio of vinyl aromatic hydrocarbon to conjugated diene is 10/90~36/64, and the melt flow is 0.1~
This invention relates to a laminate product characterized in that it uses a block copolymer layer of conjugated diene and vinyl aromatic hydrocarbon with a rate of 20 g/10 min. The present invention will be explained in detail below. The material constituting the laminate of the present invention is composed of two or more different materials selected from thermoplastic resin, thermosetting resin, vulcanized rubber, paper, metal, glass, etc. The laminate is characterized in that at least one layer contains an acrylonitrile resin containing % by weight or more as a material of the laminate. In the present invention, different materials include materials of the same type but different compositions. As the thermoplastic resin, styrene-butadiene block copolymer resin (styrene content 60% by weight)
above), polystyrene, impact-resistant rubber-modified styrene polymer, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, etc. polystyrene resin, polyethylene,
Copolymers of ethylene containing 50% by weight or more of ethylene and other monomers copolymerizable with it, such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers and their hydrolysates, ethylene-acrylic acid Polyethylene resins such as ionomers and chlorinated polyethylene, polypropylene,
Copolymers of propylene containing 50% by weight or more of propylene and monomers copolymerizable with it, such as propylene-ethylene copolymers, propylene-
Polypropylene resins such as ethyl acrylate copolymer and chlorinated polypropylene, polybutene
1. Polyethylene resin that is a copolymer of butene-1 and other monomers copolymerizable with it, polyvinyl chloride, polyvinylidene chloride, vinyl chloride containing 50% by weight or more of vinyl chloride and/or vinylidene chloride and/or polyvinyl chloride resin which is a copolymer of vinylidene chloride and other monomers copolymerizable with it, vinyl acetate containing 50% by weight or more of vinyl acetate and other copolymerizable monomers. Polyvinyl acetate resins and their hydrolysates, which are copolymers of Polyacrylate resins that are copolymers with copolymerizable monomers, polymers of acrylonitrile and/or methacrylonitrile, and copolymers with other copolymerizable monomers containing 50% by weight or more of these acrylonitrile monomers. Acrylonitrile-based resins that are polymers, linear polymers in which the structural units of the polymer are bonded by repeating amide group bonds, such as ε
-ring-opening polymers of aminocaprolactam and ω-aminolaurolactam, condensation polymers of ε-aminoundecanoic acid, hexamethylenediamine and adipic acid,
Polyamide resins such as condensation polymers with dihydrochloric acid such as sebabasic acid, linear polymers in which the constituent units of the polymer are bonded by repeated ester bonds,
For example, polyester resins that are condensates of dibasic acids such as phthalic acid and isophthalic acid or derivatives thereof and glycol components such as ethylene glycol, propylene glycol, butylene glycol, polyphenylene ether resins, or vinyl-substituted resins. Polyacetal resins such as grafted polyphenylene ether resins, polyphenylene sulfide resins, polyoxymethylenes, copolymers of trioxane and alkylene oxide, etc., in which the structural unit of the polymer is carbonic acid Linear polymers bonded by repeating ester-type bonds, such as those obtained by the reaction of phosgene with dihydroxy compounds such as 4,4'-dihydroxydiphenylalkane, 4,4'-dihydroxydiphenyl sulfide, etc. or polycarbonate resins such as polymers obtained by transesterification of the dihydroxy compound and diphenyl carbonate, polysulfone resins such as polyether sulfone and polyallylsulfone, and combinations of diisocyanate components and glycol components. Thermoplastic polyurethane resin obtained by polyaddition reaction, trans polybutadiene,
Part or all of the hydrogen in polybutadiene resins such as 1,2-polybutadiene, polyacrylate resins that are polycondensation polymers consisting of bisphenol A and phthalic acid components, and chain hydrocarbon polymer compounds is replaced with fluorine. Any thermoplastic resin can be selected from among thermoplastic resins having a structure such as fluororesins, polyoxybenzoyl resins, and polyimide resins. Thermosetting resins include unsaturated polyester resins, phenolic resins, melamine resins, urea resins,
Epoxy resins, alkyd resins, furan resins, ketone resins, benzoguanamine resins, etc. can be used. As the vulcanized rubber, natural rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, polychloroprene rubber, and vulcanized products of compositions of these rubbers and various fillers can be used. In the present invention, paper refers to materials commonly referred to as paper, such as cellophane and parchment paper (sulfuric acid paper).
including. Metals include iron, aluminum, copper, brass,
Tin, zinc and alloys containing them are applied to the laminate of the present invention in the form of plates or foils. Furthermore, various kinds of hard and soft glasses can be used as the glass. The laminate of the present invention includes not only a laminate made of two types of materials but also a multilayer laminate made of three or more types of materials. The materials to be laminated may be surface-treated in advance. In the present invention, the block copolymer described later has particularly excellent adhesion to acrylonitrile resins. Although acrylonitrile resins have extremely good gas barrier properties, they have poor adhesion and have not been able to produce satisfactorily bonded laminates. However, according to the present invention, a laminate product having excellent gas barrier properties and peel resistance can be obtained by laminating the resin and a block copolymer described later as an adhesive layer. The other materials to be laminated are preferably thermoplastic resins other than acrylonitrile resin in order to exhibit the characteristics of each material. The block copolymer used as the adhesive layer in the laminate of the present invention has a polymer structure represented by the above general formula, where n is preferably 1 or 2. If n exceeds 3, it is not preferred because the adhesive strength will be poor. In the present invention, A and A' are vinyl aromatic hydrocarbon polymer blocks, and B and A' are vinyl aromatic hydrocarbon polymer blocks.
B' is a polymer block mainly composed of conjugated diene. Here, a polymer block mainly composed of conjugated diene is defined as one in which the content of conjugated diene is 50% by weight or more,
Preferably it is a polymer block of 70% by weight or more. When B and/or B' are copolymerized with vinyl aromatic hydrocarbons, the vinyl aromatic hydrocarbons may be distributed uniformly or in a tapered manner. In addition, if a copolymer portion of a vinyl aromatic hydrocarbon and a conjugated diene with a vinyl aromatic hydrocarbon content exceeding 50% by weight exists between A or A' and B or B', the The polymer part is B
Or it shall be included in B' (However, if the copolymer part is included in B or B', the content of conjugated diene in the block part including the copolymer part must be 50% by weight or more. ). In the present invention, the content of polymer block B in the block copolymer molecular chain is 3 to 50% by weight,
Preferably it is 5 to 40% by weight, and block B
- The content of block A in part A is 25 to 85% by weight, preferably 30 to 80% by weight. If the content of blocks B and A is outside the above range, the adhesive strength will decrease, which is not preferable. In the block copolymer used in the present invention, the weight ratio of vinyl aromatic hydrocarbon to conjugated diene is 10/90 to 36/64, preferably 15/85 to 33/67. If the weight ratio of vinyl aromatic hydrocarbon to conjugated diene is outside the above range, adhesive strength will decrease. Furthermore, the block copolymer used in the present invention has a melt flow of 0.1 to 20 g/
10 min, preferably 1 to 15 g/10 min. When the melt flow is less than 0.1 g/10 min, melt fluidity and solubility are poor, resulting in poor processability when producing a laminate. On the other hand, if it exceeds 20 g/10 min, the adhesive strength will be poor, and in the case of coextruded laminates, the adhesive layer may protrude from the edges of the laminate, resulting in uneven adhesive strength, which is not preferable. The melt flow referred to in the present invention refers to the temperature
Values measured at 200°C and a load of 5 kg (condition G). In the block copolymer used in the present invention, the average molecular weight of block A should be larger than that of block A' in order to obtain a laminate with good adhesive strength, especially when the peeling state is cohesive failure. preferable. Specifically, it is recommended that the average molecular weight of block A be at least 1.1 times, preferably 1.3 to 5 times, the average molecular weight of block A'. In order to keep the average molecular weight ratio of block A and block A' within the above range, the quantitative relationship of the vinyl aromatic hydrocarbons used to form blocks A and block A' should be within the above range. . The block copolymer used in the present invention is prepared by arranging monomers corresponding to polymer blocks A, A' and B, B' in the order of the polymer structural formula shown above using an organic lithium compound as a catalyst in a hydrocarbon solvent. It can be produced by sequential polymerization according to the following steps. Vinyl aromatic hydrocarbons used in the production of the block polymer used in the present invention include styrene, o-methylstyrene, p-methylstyrene,
Among them, p-tert-butylstyrene, 1,3 dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc., and styrene is particularly common. These may be used not only as a single type but also as a mixture of two or more types. Examples of conjugated dienes include diolefins having 4 to 8 carbon atoms and a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-butadiene. dimethyl 1,3
Examples include butadiene, 1,3-pentadiene, 1,3-hexadiene, and particularly common ones include 1,3-butadiene and isoprene. These may be used not only as a single type but also as a mixture of two or more types. The block copolymer of the present invention can be subjected to hydrogenation, halogenation, hydrogen halogenation, or chemical reaction within a range that does not impair its basic properties, such as moldability, mechanical strength, adhesive properties, etc. Therefore, various modifications such as introduction of carboxyl groups, ester groups, nitrile groups, sulfonic acid groups, amino groups, etc. may be carried out. Furthermore, the block copolymer used in the present invention can be blended with a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene that does not meet the requirements stipulated in the present invention to improve moldability, etc. However, in order not to impair the properties of the block copolymer used in the present invention, the blending amount is 50% by weight.
It is preferable to do the following. The block copolymers used in the present invention include coumaron/indene resin, phenolic resin, p-tert-butylphenol/acetylene resin, phenol/formaldehyde resin, terpene/phenolic resin, polyterpene resin, xylene/formaldehyde resin, synthetic Polyterpene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, monoolefin and olefin oligomer, hydrogenated hydrocarbon resin, hydrocarbon tackifying resin, polybutene, polyhydric alcohol ester of rosin, hydrogenated rosin , hydrogenated rosin, ester of hydrogenated rosin and monoalcohol or polyhydric alcohol,
Turpentine tackifier, low polymerization degree polystyrene,
Block copolymer of low polymerization degree polybutadiene etc.
It can be used by adding up to 100 parts by weight to 100 parts by weight. Further, the above-mentioned thermoplastic resins, natural rubber, synthetic rubber, plasticizers, organic peroxides, antioxidants, fillers, ultraviolet absorbers, etc. may be added insofar as the adhesiveness is not deteriorated. The method of adhering two or more different materials as adherends using the block copolymer described above is not particularly limited and can be any commonly used method. That is, an extrusion laminate in which the block copolymer defined in the present invention is heated and melted using an extruder and then pressed into a film or sheet form to an adherend, and the block copolymer used in the present invention and the adherend are A coextrusion method in which the block copolymer specified in the present invention is made into a film or sheet in advance, and the block copolymer specified in the present invention is made into a film or sheet, which is then bonded to the adherend and heated using a heat press or the like. A press method in which the block copolymer specified in the present invention is heated and melted and applied to an adherend formed into a film by a method such as an extrusion method or a casting method, and a hot lamination method in which the block copolymer specified in the present invention is A dry lamination method in which the polymer is dissolved in a solvent, applied to the adherend, and then the solvent is released and bonded under heat.The block copolymer specified in the present invention is dispersed in water using an appropriate emulsifier. A method such as a wet lamination method is used, but methods other than these may also be used. In particular, the above-mentioned hot-melt bonding methods such as extrusion lamination, coextrusion, hot lamination, and pressing can be applied to the block copolymer specified in the present invention at a temperature of 100 to 250°C for about 2
Since sufficient adhesive strength can be obtained by applying a pressure of 2 to 100 kg/cm ² for 20 minutes to 20 minutes, the adhesive operation is easy and particularly preferred. In particular, in the coextrusion lamination method, a multilayer laminate molded product can be easily formed by multilayer T-die extrusion molding, multilayer inflation molding, multilayer blow molding, etc., so it is adopted as a useful method for obtaining the laminate product of the present invention. can. Furthermore, the block copolymer defined in the present invention is extremely easily soluble in general-purpose solvents such as toluene, xylene, cyclohexane, ethyl ether, tetratrophuran, butyl acetate, etc., and gives a low viscosity solution at a concentration of 5 to 70%. Therefore, the dry lamination method is also one of the suitable methods. The thickness of the block copolymer layer of conjugated diene and vinyl aromatic hydrocarbon that forms the adhesive is 5μ or more,
Preferably, the thickness is 10μ or more in order to provide sufficient adhesive strength. If the adhesive layer is too thick, the rigidity of the laminate will be reduced and it will be economically disadvantageous, so it is generally preferable to keep the thickness to 300 μm or less. [Effects of the Invention] The block copolymer defined in the present invention has excellent adhesion and processability, particularly in hot-melt bonding methods such as coextrusion lamination. The laminated product has excellent peel strength and a good finish. In the present invention, by combining various materials, gas barrier properties, gas permeability, waterproof properties, adhesive properties, printability, chemical resistance, antistatic properties, weather resistance, heat seal properties, impact resistance, scratch resistance, etc. A laminate having the following characteristics is obtained. In particular, the laminate of the present invention using an acrylonitrile resin as an adherend has high gas barrier properties, and can be used in various applications that take advantage of its characteristics. Laminated products using the adhesive of the present invention can be used in the form of films, sheets, packaging films for foods, pharmaceuticals, cosmetics, etc., containers, lids, materials for various molding processes such as vacuum forming and pressure forming, as well as hollow It can be used for a wide variety of purposes, including directly molding it into molded products. [Examples] Examples are shown below to explain the present invention in more detail, but these examples are for showing the excellent effects obtained by the present invention,
It is not intended to limit the scope of the invention. Examples 1 to 7 and Comparative Examples 1 to 11 Using n-butyllithium as a catalyst in a solvent containing cyclohexane as a main component under a nitrogen atmosphere (for example, in the case of block polymer 1, 0.1 parts by weight per 100 parts by weight of the total monomers used) parts by weight), 1st
₁ part of monomer B was polymerized at about 70° C. according to the monomer amounts shown in the table, and after the monomers were substantially completely polymerized, ₁ part of monomer A was added and polymerized. After the added monomers are substantially completely polymerized, the monomers of B ₂ and A ₂ parts are sequentially polymerized in the same manner to form a block having a polymer structure of B ₁ -A ₁ -B ₂ -A ₂ . A copolymer was obtained. Each monomer was used after being diluted with a solvent so that the monomer concentration was 20% by weight. Each of the obtained block copolymers contained 2,4-di-tert-butyl-p as a stabilizer.
-0.5 parts by weight of each of cresol and trisnonyl phosphate were added to 100 parts by weight of the block copolymer. The ratio of the average molecular weights of the portions corresponding to blocks A ₁ and A ₂ in the resulting block copolymer was approximately the same as the quantitative ratio of the monomers used to form blocks A ₁ and A ₂ , respectively. Next, two 30 m/m extruders (extruder and) and one 25 m/m extruder (extruder) were used. omitted) and extruded at about 220°C, and each of the block copolymers shown in Table 1 was fed as an adhesive layer to the extruder, and the extruder was heated at about 200°C.
The extruder was supplied with acrylonitrile resin (a copolymer of 75 parts by weight of acrylonitrile and 25 parts by weight of methyl acrylate) and extruded at about 200°C.
A coextruded laminate was obtained with a layer thickness of approximately 0.5 mm, an acrylonitrile layer thickness of approximately 0.2 mm, and an intermediate adhesive layer thickness of approximately 50 μm. In Comparative Example 3, the block copolymer had poor fluidity and could not be extruded using an extruder to produce a good adhesive layer. Further, in Comparative Example 4, the melt viscosity of the block copolymer was low and there was protrusion from the end portion of the coextrusion lamination process, resulting in a poor finish. Next, the peel strength of each of the obtained laminates was measured, and it became clear that the laminate of the present invention had extremely excellent peel strength. The results are shown in Table 1.
In addition, in Comparative Example 4, there was uneven peeling and the adhesion state was not good. Furthermore, as a comparative example, it has a (A ₁ −B ₂ −) ₄ Si structure,
Styrene content is 30% by weight, melt flow is 10
A laminate was obtained in the same manner as in Example 1 using a block copolymer of g/10 min as an adhesive layer. The peel strength of this laminate was less than 1.0 Kg/25 mm, which was inferior to the laminate of the present invention.

【table】

[Table] Examples 8 to 11 The thermoplastic resin shown in Table 2 was supplied to the extruder and extruded, and block copolymer 1 was supplied to the extruder and extruded, and block copolymer 1 was extruded. A laminate product to be used as an adhesive layer was obtained. The thickness of each thermoplastic resin layer was adjusted to approximately 0.1 mm.
The adhesive layer was adjusted to have a thickness of approximately 100μ. Next, when the peel strength of each laminate was measured, the peel strength in all cases exceeded 1.0 Kg/25 mm, indicating that the laminate had good adhesive properties. In particular, in Examples 8 and 9, 2.5Kg/25mm and 2.3
The peel strength was Kg/25mm.

【table】

[Table] Example 12 In Example 8, as the adhesive layer polymer,
100 parts by weight of block copolymer 6 to 50 parts of terpene resin (YS Resin A-800, manufactured by Cheap Crude Oil)
Example 8 except that the composition was added in parts by weight.
A laminate was obtained in the same manner. The resulting laminates each exhibited excellent peel strength similar to Example 8. Example 13 8 parts by weight, 30 parts by weight, and 30 parts by weight of butadiene were used in steps 1, 3, and 5 of polymerization, respectively, and 12 parts by weight and 10 parts by weight of styrene were used in steps 2, 4, and 6, respectively. part, 10 parts by weight, B-A
-(B-A) ₂ structure, melt flow is 5g/
A block copolymer was obtained for 10 min. Next, a laminate similar to that of Example 1 was prepared using the block copolymer obtained above as an adhesive layer. The peel strength of this laminate exceeded 2 kg/25 mm.

Claims (1)

[Scope of Claims] 1. In a laminate made of two or more different materials, at least one layer of an acrylonitrile resin containing 50% by weight or more of an acrylonitrile monomer is used as the material of the laminate, and the acrylonitrile resin The polymer structure has the general formula B-A-(B'-A')n (In the above formula, A and A' are vinyl aromatic hydrocarbons. The polymer blocks B and B' are polymer blocks mainly composed of conjugated dienes. n is an integer from 1 to 3.) The content of polymer block B in the molecular chain of the block copolymer The content of block A in the block B-A portion is 25 to 50% by weight.
85% by weight, the weight ratio of vinyl aromatic hydrocarbon to conjugated diene is 10/90~36/64, and the melt flow is 0.1~
A laminate product characterized by using a block copolymer layer of conjugated diene and vinyl aromatic hydrocarbon at a rate of 20g/10min. 2. The laminate product according to claim 1, wherein the laminate products are laminated by a hot melt adhesive method. 3. The laminate product according to claim 2, wherein the two or more different materials are made of thermoplastic resins, and the laminate product is laminated by a coextrusion lamination method.