JPH0246612B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an adhesive resin composition that not only has good adhesion to both olefin resins (especially propylene resins) and styrene resins, but also has excellent blocking resistance. . More specifically, (A) at least one propylene selected from the group consisting of a propylene homopolymer, a random copolymer of propylene and ethylene or an α-olefin, and a block copolymer of propylene and ethylene or an α-olefin. system polymer, (B) copolymer of ethylene and vinyl acetate, (C)
It relates to an adhesive resin composition consisting of an impact-resistant styrenic polymer and (D) a block copolymer of a vinyl aromatic compound and a conjugated diene, and has good properties against both olefin resins and styrene resins. The purpose is to provide a resin composition that not only has adhesive properties and has good adhesion to these molded objects (e.g., films, sheets, foams), but also has excellent blocking resistance. be. Conventional technology Synthetic resins, which are widely used as packaging materials, have recently been developed into multilayered structures that combine the properties of individual resins in order to satisfy all of the performance requirements as the uses for packaging products have diversified. Products are being studied and used in the market. Films, sheets, and foams obtained by molding styrenic resins have the advantage of being relatively low cost, in addition to the good rigidity inherent to styrenic resins and the molding process. Currently, it is widely used as various containers such as cups and boxes.
It has the disadvantage of poor heat resistance and oil resistance. On the other hand, as is well known, olefin resins have relatively good oil resistance, and among these olefin resins, high-density polyethylene and propylene resins in particular have better heat resistance than styrene resins. However, there is a problem that it is inferior to styrene resin in terms of rigidity. For these reasons, various multilayer structures of olefin resins and styrene resins have been proposed in order to improve the oil resistance and heat resistance of various molded products made of styrene resins. Originally, olefin resin and styrene resin were
To obtain these multilayer structures, an adhesive layer is essential between them, since their mutual adhesion is very poor. Conventionally, a copolymer of ethylene and vinyl acetate (hereinafter referred to as "EVA") has been used as this adhesive layer, but EVA generally has good adhesive properties with olefin resins (especially ethylene polymers). However, in order to obtain good adhesion with styrenic resins, the vinyl acetate content in EVA must be approximately 35% by weight or more, and such EVA has a strong vinyl acetate odor. It has poor thermal stability, and there are also problems with extrusion stability. In order to improve these problems, for example, butadiene-styrene copolymers (for example, JP-A-49-33973, JP-A-55-126449), styrene-isoprene blocks are used as the adhesive layer of the multilayer structure. Copolymer (JP-A-55-14209), ethylene-
Acrylic acid alkyl ester copolymer (Japanese Unexamined Patent Publication No. 1983)
-85751), graft modified products of unsaturated carboxylic acids of vinyl aromatic compound-conjugated diene compound block copolymers (for example, block copolymers of styrene and butadiene or isoprene) (JP-A-55-87551). ) have been proposed. However, although these adhesive layers exhibit fairly good adhesion with styrene resins, their adhesion with olefin resins (especially propylene resins) is insufficient, especially when the total thickness is 0.2 mm or less,
In addition, when the molding speed of composite is fast, the adhesion with propylene resin and styrene resin is not necessarily satisfactory, and the value of the lower one of adhesion is at most 100 to 130 g/15 mm, which is not practical. It is insufficient in this respect. With this level of adhesion, it is possible to fill a variety of containers molded with multilayered structures obtained using these adhesive layers with, for example, food, and heat them at a temperature of 100 to 130°C using, for example, a microwave oven. When subjected to high heat treatment for several minutes, peeling of the adhesive layer is observed, resulting in a significant decrease in functionality and commercial value. Based on these facts, some of the inventors of the present invention have found that they do not have these drawbacks (problems), that is, they can be used for both styrene resin molded products (e.g. foams and sheets) and olefin resin molded products in a well-balanced manner. As a result of various studies on obtaining a resin composition with practical adhesiveness (at least 150 g/15 mm, preferably 200 g/15 mm or more), we found that (A) a propylene-based polymer (a propylene homopolymer, a propylene-based polymer) (B) a copolymer of ethylene and vinyl acetate with a vinyl acetate content of 5 to 35% by weight; and (C) a block copolymer of a vinyl aromatic compound and a conjugated diene. It has been discovered and previously proposed that an adhesive resin composition comprising a copolymer is a composition that can solve all of the above-mentioned various properties. However, in order to obtain a styrene resin multilayer structure, for example, when obtaining a two-layer, two-layer film consisting of the adhesive resin composition layer and the propylene resin layer, the adhesive resin composition and the propylene resin are mixed together. Because the adhesive resin composition itself has good thermal adhesion and is slightly sticky, this two-layer, two-layer multilayer film has excellent anti-blocking properties between the adhesive resin composition layer surface and the propylene resin layer surface. Furthermore, it was found that when the multilayer film was rewound and thermally bonded to the styrene resin, the multilayer film was uneven in tension and had transportation troubles, and was not smooth and did not have good thermal bonding. Problems to be Solved by the Invention From the above, the present invention does not have these drawbacks (problems), and is suitable for both molded products of styrene resins and molded products of olefin resins (particularly propylene resins). The object of the present invention is to obtain a resin composition that not only has a well-balanced adhesive property and has the above-mentioned practical adhesion properties, but also has good heat-resistant blocking properties and is free from tension unevenness and transportation troubles when thermally bonded. . Means and Effects for Solving the Problems According to the present invention, these problems are solved by (A) propylene homopolymers, random copolymers of propylene and ethylene or α-olefins, and propylene and ethylene or - at least one propylene polymer selected from the group consisting of block copolymers with olefins; (B) a vinyl acetate content of 5 to 35% by weight;
and melt flow rate (measured under conditions 4 according to JIS K6730, hereinafter referred to as "MFR")
a copolymer of styrene and vinyl acetate with a weight ratio of 0.5 to 40 g/10 min (hereinafter referred to as "ethylene-vinyl acetate copolymer"), (C) impact-resistant styrenic polymer, and (D) vinyl aromatic. A composition consisting of a block copolymer of a compound and a conjugated diene, in which the proportion of the propylene polymer in the composition is 1 to 20% by weight, and a block copolymer of a vinyl aromatic compound and a conjugated diene. An adhesive resin composition in which the copolymer has a composition ratio of 1 to 25% by weight, the impact-resistant styrene polymer has a composition ratio of 5 to 30% by weight, and the remainder is an ethylene-vinyl acetate copolymer. It can be solved by things. The present invention will be specifically explained below. (A) Propylene-based polymer The propylene-based polymer used in the present invention includes a propylene homopolymer, a random copolymer of propylene and "ethylene or α-olefin" (hereinafter referred to as "comonomer"), and a random copolymer of propylene and a comonomer. selected from block copolymers of The copolymerization proportion of said comonomers, both in random and block copolymers, is usually at most 20% by weight, especially 15% by weight.
The following are desirable. In addition, the number of carbon atoms in the comonomer is generally at most 12, and typical examples include ethylene, butene-1, hexene-1, and 4-carbon.
Examples include methylpentene-1, with ethylene being particularly preferred. The melt flow rate (measured according to JIS K6758, hereinafter referred to as "MFR") of the propylene polymer is usually 0.01 to 100 g/10
minutes, preferably 0.05 to 80 g/10 minutes, particularly preferably 0.1 to 50 g/10 minutes. If the MFR of the propylene polymer is less than 0.01g/10 minutes,
When producing the composition of the present invention, not only is the kneading property poor, but it is also difficult to obtain a uniform composition, resulting in variations in adhesive properties.
On the other hand, if a propylene-based polymer exceeding 100 g/10 minutes is used, not only the thermal stability of the resulting composition will be poor, but also the extrusion process stability will be poor. (B) Ethylene-vinyl acetate copolymer Also, ethylene-vinyl acetate copolymer used in the present invention
The vinyl acetate content (copolymerization ratio) of the vinyl acetate copolymer is 5 to 35% by weight, preferably 10 to 30% by weight, and particularly preferably 15 to 25% by weight. If the copolymerization ratio of vinyl acetate in the ethylene-vinyl acetate copolymer is less than 5% by weight, the adhesion to propylene polymers and styrene polymers will be poor. On the other hand, when an ethylene-vinyl acetate copolymer with a copolymerization ratio exceeding 35% by weight is used, the odor of vinyl acetate is noticeable as described above.
Lacks thermal stability and extrusion stability. MFR of this ethylene-vinyl acetate copolymer
(measured according to JIS K6730) is 0.5 to 40g/
10 minutes, preferably 1 to 30 g/10 minutes, particularly preferably 2 to 25 g/10 minutes. Ethylene-
If the MFR of the vinyl acetate copolymer is less than 0.5 g/10 minutes, the kneading properties of the propylene polymer and the block copolymer of styrene and conjugated diene will be poor, and it will be difficult to obtain a homogeneous composition. Variations occur in adhesion. On the other hand, MFR
If an ethylene-vinyl acetate copolymer with a temperature exceeding 40 g/10 minutes is used, the resulting composition will have a high melt flow rate and poor molding stability. (C) Impact-resistant styrenic polymer Furthermore, the impact-resistant styrenic polymer used in the present invention is butadiene homopolymer rubber, butadiene-styrene block copolymer rubber, or butadiene-styrene copolymer rubber (hereinafter referred to as It can also be produced by graft polymerizing a styrene monomer (referred to as "SBR"). Graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, aqueous suspension polymerization, and methods of combining these graft polymerization methods (for example, bulk polymerization followed by aqueous suspension polymerization). Generally, the amount of the rubber used to produce 100 parts by weight of the graft polymer (high impact styrenic polymer) is 1.0 to 20 parts by weight (relatively large amount of the rubber is mixed with styrene). (Although a styrene homopolymer may be mixed into the graft polymer obtained by grafting, the amount of rubber used in this case is calculated based on the mixture). The molecular weight of the styrene bonded to the rubber as a graft chain is usually
500 to 500,000, particularly preferably 500 to 300,000. In general, it is rare for styrene to be completely bonded to rubber, and there are grafts and homopolymers of styrene that are not bonded to rubber. The homopolymer is used as is without separation. Additionally, the Mooney viscosity of the rubber is generally 20 to 140.
and those of 30 to 120 are particularly suitable. Furthermore, a composition comprising the above-mentioned rubber (composition ratio 1 to 20% by weight) and a styrene homopolymer can also be used. The melt flow index (measured according to JIS K6870 method, hereinafter referred to as "MFI") of this impact-resistant styrenic polymer is not particularly specified, but is usually 0.1 to 50 g/10 minutes, and 0.2
~50g/10min is preferable, especially
0.5 to 30 g/10 minutes is suitable. MFI
If it is less than 0.1 g/10 minutes, the kneading properties will be poor and it will be difficult to obtain a uniform composition. on the other hand,
If an impact-resistant styrenic polymer with an MFI exceeding 50 g/10 minutes is used, the resulting composition will have a high melt flow rate and poor molding stability. (D) Block copolymer of a vinyl aromatic compound and a conjugated diene The block copolymer of a vinyl aromatic compound and a conjugated diene used in the present invention is a combination of a conjugated diene compound such as butadiene or isoprene and styrene, α- It is a block copolymer with a vinyl aromatic compound such as methylstyrene or vinyltoluene (among which styrene is preferred), and the forms of the block include single block copolymer, teleblock copolymer, and radial teleblock copolymer. Examples include block copolymers, multi-block copolymers, and any of these block copolymers may be used. The copolymerization ratio of the vinyl aromatic compound in the block copolymer is usually 5.
-85% by weight, preferably 5-80% by weight,
Particularly suitable is 10 to 80% by weight. If the copolymerization ratio of the vinyl aromatic compound is less than 5% by weight, the adhesiveness with the styrene resin will be poor. Meanwhile, 85% by weight
If it exceeds 100%, the adhesion of the propylene polymer will be poor. Furthermore, the melt index (measured according to ASTM D1238 under conditions E, hereinafter referred to as "MI") of this block copolymer is 20 g/10
minutes or less, preferably 10 g/10 minutes or less, and particularly preferably 0.01 to 10 g/10 minutes. M.I.
If a block copolymer exceeding 20 g/10 minutes is used, the resulting composition will have a high melt flow rate and poor molding stability. (E) Composition ratio The composition ratio of the propylene polymer in the composition obtained by the present invention is 1 to 20% by weight,
2 to 20% by weight is preferred, particularly 5 to 20% by weight. If the proportion of the propylene polymer in the composition is less than 1% by weight, not only the resulting composition will have poor adhesion to the propylene resin, but also the heat resistance of the composition will be poor.
On the other hand, if it exceeds 20% by weight, the adhesion of the resulting composition to the styrene resin will decrease. That is, the purpose of blending the propylene polymer in the above composition range in the present invention is to provide adhesiveness with the propylene resin and further improve heat resistance. In addition, the composition ratio of the block copolymer of a vinyl aromatic compound and a conjugated diene is 1 to 25% by weight, preferably 2 to 25% by weight, especially 5 to 25% by weight.
25% by weight is preferred. Even if the proportion of the block copolymer in the composition is less than 1% by weight or more than 25% by weight, the adhesion to styrene resins is particularly poor. Further, the composition ratio of the impact-resistant styrenic polymer is 5 to 30% by weight, preferably 10 to 25% by weight, and particularly preferably 15 to 25% by weight. If the composition ratio of the impact-resistant styrenic polymer is less than 5% by weight, the effect of improving the blocking resistance of the resulting composition is poor. On the other hand, if the amount exceeds 30% by weight, the adhesion of olefin resins and styrene resins will be poor. From the above, the composition ratio of the ethylene-vinyl acetate copolymer in the composition of the present invention is 25
~93% by weight, preferably 30-84% by weight,
Particularly suitable is 30 to 75% by weight. In the present invention, the reason why the ethylene-vinyl acetate copolymer is blended within the above composition ratio range is to simultaneously improve the adhesive strength between the olefin resin and the styrene resin, and even if the upper limit is exceeded, the lower limit Even if it is less than that, the adhesion with these resins is not good. (F) Composition production, molding method, etc. In producing the composition of the present invention, the above-mentioned propylene polymer, ethylene-vinyl acetate copolymer, high-impact styrene polymer, and vinyl aromatic compound are conjugated. The block copolymer with diene may be uniformly mixed within the above composition ratio range. At this time, heat or oxygen stabilizers, lubricants, plasticizers, fillers, antistatic agents, flame retardants, pigments (colorants) may be used within the range that does not essentially lose the properties of the composition of the present invention. Additives such as tackifiers and adhesion agents may also be added. The mixing method is a Henschel mixer, which is widely used in the field of thermoplastic resins.
Dry blending may be performed using mixers such as ribbon mixers and tumblers, or melt kneading may be performed using mixers such as Banbury mixers, kneaders, roll and screw extruders. Among these, the latter method of melt kneading is more preferable as a means of obtaining a more uniform composition, and from an economical point of view, mixing using a screw extruder is preferably employed. Further, if necessary, the product may be passed through a screw extruder two or more times. Whether the composition of the present invention is melt-kneaded or molded from the composition, the propylene polymer, ethylene-vinyl acetate copolymer, and impact-resistant It is necessary to conduct the process at a temperature at which the polystyrene polymer and the block copolymer of a vinyl aromatic compound and a conjugated diene are melted. However, it must be carried out at a temperature at which these components do not decompose thermally. Therefore, the above treatments (melt kneading, molding, etc.) must be carried out at a temperature range of 160 to 300°C (preferably 160 to 250°C). As mentioned above, the adhesive resin composition of the present invention obtained in this manner has good adhesion to styrene resins and olefin resins (especially propylene resins), which will be described later. It can be used as an adhesive material for manufacturing a multilayer structure with various molded bodies described below, each made of a resin. The multilayer structure obtained by interposing the adhesive resin composition of the present invention between an olefin resin and a styrene resin has the heat resistance and oil resistance (vegetable oil, animal oil, mineral oil) that the olefin resin has. The glossiness and high hardness of styrenic resins can be exhibited. The multilayer structure and its manufacturing method will be described in detail below. (G) Manufacture of multilayer structure (1) Multilayer structure The adhesive resin composition of the present invention has excellent adhesion to both styrene resins and olefin resins as described above, so it can be used in various laminates ( multilayer structures) can be manufactured. Typical examples of the structure of a multilayer structure include a two-layer structure consisting of either an olefinic resin layer or a styrene resin layer and an adhesive resin composition layer of the present invention; A multilayer structure consisting of three types and three layers with the adhesive resin composition layer interposed between the resin layer and one or more olefin resin layers and one or more styrene resin layers, but the total of these is three or more layers. and a multilayer structure in which the adhesive resin composition layer of the present invention is interposed between an olefin resin layer and a styrene resin layer. Typical examples of the olefin resin used to constitute this olefin resin layer include the above-mentioned propylene polymer, ethylene homopolymer, ethylene and α-olefin (usually has 3 to 12 carbon atoms), or vinyl Examples include copolymers with compounds (for example, vinyl acetate) (the copolymerization ratio of α-olefin is generally at most 20% by weight, and the copolymerization ratio of vinyl compounds is usually 30% by weight or less). Typical examples of ethylene resins used to form the styrene resin layer include styrene homopolymers and copolymers of styrene and vinyl compounds (the copolymerization ratio of vinyl compounds is generally at most 50% by weight) and the above-mentioned impact-resistant styrenic polymers. In producing a multilayer structure, these olefinic resins and styrene resins may be used alone or in a composition of two or more. Furthermore, compositions consisting of other thermoplastic resins and/or elastomers or various additives (for example, various stabilizers, fillers, antistatic agents, etc.) may be added to the extent that the properties of each resin are not essentially impaired. , colorant). The thickness of the adhesive resin composition layer constituting the multilayer structure is generally 1 micron or more,
The thickness is preferably 2 microns or more, particularly 5 microns or more. Further, the thickness of each of the olefin resin layer and the styrene resin layer is usually 5 microns or more, preferably 10 microns or more, and particularly preferably 20 microns or more. The upper limit of the thickness of each of the above layers is not particularly limited depending on the use of the multilayer structure obtained. Typically either layer is 50mm or less. Further, the styrene resin layer may be a foamed material (the expansion ratio is generally 100 times or less, preferably 50 times or less). In addition, the expansion ratio of olefin resin is usually 40 times or less (preferably
30 times or less). (2) Manufacturing method (molding method) To manufacture this multilayer structure, a method generally used for manufacturing laminates may be applied. In addition, in the following explanation,
Olefin resin, styrene resin, and adhesive resin composition refer to those that have not been pre-molded into the following molded products, and "PO base material" is obtained by pre-molding olefin resin. Molded products (e.g., films, sheets, foams), "PS base materials" refer to molded products (e.g., films, sheets, foams) obtained by pre-molding styrene resin, and "composition base materials". ” refers to a molded product (eg, a film, a sheet) obtained by molding the adhesive resin composition of the present invention. As for the molding method, first, an extruder equipped with a T-die is used to form an adhesive resin composition, or two extruders and a two-layer coextrusion die are used to form a styrene resin and an adhesive resin composition into a PS base. Sand Germany lamination method (so-called polysand method) involves melt-extruding the adhesive resin composition between the polysand material and the PO base material.Secondly, after extrusion lamination of the adhesive resin composition onto the PS base material, this laminate is further coated with olefin. There are two methods: extrusion lamination of an adhesive resin composition and extrusion lamination of an adhesive resin composition onto a PO base material, and then extrusion of a styrene resin onto the laminated product (so-called double lamination method). Furthermore, a laminate of two types and two layers, an olefin resin layer and an adhesive resin composition layer, is manufactured in advance (methods include coextrusion molding, extrusion lamination of an adhesive resin composition onto a PO base material, etc.). By laminating this laminate with a PS base material, a laminate of three types and three layers consisting of an olefin resin layer and a styrene resin layer with an adhesive resin composition layer in the middle etc. can be manufactured in advance. (Methods include a coextrusion molding method and a polycide method in which an adhesive resin composition is melt-extruded between a PS base material and a PO base material.) There is also a method of laminating each base material. Examples of methods for laminating the above-mentioned laminate to the PS base material include the generally practiced thermal adhesion method and the Sand-German lamination method (polysand method) using the same method as described above. Thermal bonding methods include methods that use generally known heat supply means such as high-pressure steam, electric heat, or rolls with heated oil circulating, or methods that use an oven equipped with an infrared heater, a far-infrared heater, or an electric heater. As an economical method, thermal bonding using a roll is preferred. All of the above methods need to be carried out at a temperature of 160°C or higher. If the temperature is lower than 160°C, the adhesion to the base material will be poor, and this will be unsatisfactory for practical use. Among these methods, there is no need to specify an upper limit temperature, but if the propylene polymer that forms the surface layer is completely melted, the appearance or commercial value will deteriorate, so it is recommended to set it below 200°C (preferably, (below 190℃)
It is desirable to carry out the However, since a continuous bonding process is normally employed, the optimum conditions are determined by the speed line or the total thickness of the laminate. In addition, in performing the above-described bonding, the base material may be pretreated (for example, preheated) as is generally practiced in order to further improve the adhesion to the base material.
In addition, using another lamination method, the Sand-German tylamination method, and an extruder equipped with a T-die between the styrene resin base material and the laminate,
This is a method of bonding by melt-extruding a styrenic polymer (for example, high-impact polystyrene), during which time the molten styrenic polymer layer is bonded. It goes without saying that the laminate is the adhesive resin composition of the present invention (in the case of the laminate of two types and two layers described above) and a styrene polymer (in the case of the laminate of three types and three layers described above). The methods for producing a multilayer structure have been described above, and among these production methods, a multilayer structure is obtained by bonding a laminate comprising the adhesive resin composition of the present invention and a propylene polymer to a base material. In this case, as mentioned above, the adhesive resin composition of the present invention is significantly superior in blocking resistance compared to conventionally known compositions. When laminated by a roll method, the slipperiness (blocking resistance) of the propylene polymer surface of the laminate film and the adhesive resin composition surface of the present invention is excellent, making it difficult for local tension unevenness to occur during lamination. It has the advantage of being able to obtain a wrinkle-free multilayer structure with an excellent appearance. The multilayered structure obtained in this way may be used in the form of a sheet, but it can also be formed into a desired container depending on the intended use. The multilayer structure obtained in this way not only has good heat resistance but also excellent oil resistance when the surface layer is an olefin resin layer (especially a propylene resin layer). When it is a styrene resin, it not only has high gloss but also has excellent hardness. EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be explained in more detail with reference to Examples. In the Examples and Comparative Examples, the adhesive strength was measured using a Tensilon type tensile tester, and the peeling speed was
The resistance was determined by peeling in a direction of 180 degrees at a rate of 100 mm/min and measuring the resistance value. Further, the blocking resistance of the coextruded film was evaluated by measuring the coefficient of friction (ASTM D1894 method) between the polypropylene layer surface and the adhesive layer surface of the coextruded film. In addition, in the examples and comparative examples, the ethylene content was 2.4% by weight as a propylene-based polymer.
An ethylene-propylene random copolymer (MFR 4.1 g/10 minutes, hereinafter referred to as "PP") was used. Further, as the ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer (MFR 4.5 g/10 minutes, hereinafter referred to as "EVA") having a vinyl acetate content of 20% by weight was used. Furthermore, as a block copolymer of styrene and conjugated diene, a styrene-butadiene-styrene block copolymer (MFR 2.5) with a styrene content of 40% by weight is used.
g/10 minutes, hereinafter referred to as "SBS") was used. In addition, as an impact-resistant styrenic polymer, a graft polymer (MFR 3.0 g/10 min, hereinafter referred to as " HIPS) was used. Examples 1 to 10, Comparative Examples 1 to 7 PP, EVA, whose blending amounts are shown in Table 1,
SBS and HIPS were dry blended in advance for 5 minutes using a Henschel mixer. Each of the obtained mixtures was melt-kneaded using an extruder at a temperature of 200°C to produce a composition (pellet). This adhesive resin composition (B) and a propylene homopolymer (A) having an MFR of 10 g/10 minutes are used in a thickness composition [(B)/
(A)] was 25 microns/50 microns, and a coextruded film was prepared using a multilayer T-die film forming apparatus.
The adhesive strength between the (A) layer and (B) layer in each of the obtained coextruded films was measured. Furthermore, the coefficient of friction between the propylene homopolymer (PP) layer surface of the coextruded film and the adhesive resin composition was measured. The results are shown in Table 1. Next, each coextruded film was used to form a styrene resin sheet (PSS) with a thickness of 0.2 mm using a heated roll set at the temperature shown in Table 1.
Alternatively, a multilayer structure in which styrene resin (PS), adhesive resin composition, and propylene homopolymer are sequentially laminated by laminating with a styrene resin foam (PSP, foaming ratio of about 10 times) of the same thickness is created. Created. The adhesive strength between the styrene resin layer and the adhesive resin composition layer of the obtained multilayer structure was measured. The results are shown in Table 1. Also, for comparison, the samples used in Examples 1 to 10
EVA and SBS, ethyl acrylate content
Using a copolymer of ethylene and ethyl acrylate (EAA) having a content of 20% by weight, coextruded films with PP used in Examples 1 to 10 were prepared in the same manner.
The same evaluation as above was performed. The results are shown in Table 1.

【table】

[Table] From the results of the above Examples and Comparative Examples, the adhesive resin composition obtained by the present invention has good adhesion to both olefin resins (especially propylene resins) and styrene resins. It is clear that the adhesive resin composition and the olefin resin have good interlayer adhesion in the laminate, and that the blocking resistance is also extremely excellent. It is. Furthermore, in the case of the present invention, since the outermost layer of the resulting multilayer structure is composed of an olefin polymer with excellent oil resistance and heat resistance, the product formed into a tray etc. It is clear that it can be used in a wide variety of ways as a packaging container. Effects of the Invention The adhesive resin composition of the present invention and the laminate or multilayer structure using the composition exhibit the following effects (characteristics) including their manufacturing process. (1) The composition has good adhesion to both olefin resins and styrene resins. (2) Not only is the composition easy to manufacture, but also a laminate can be easily manufactured by coextruding the composition with a styrene resin and/or olefin resin. (3) Since the composition has excellent blocking resistance, a laminate made of styrenic resin also has good blocking resistance, and when this laminate is bonded to a base material to produce a multilayer structure, A wrinkle-free multilayer structure with good appearance can be obtained. (4) The multilayer structure of the present invention in which an olefin resin (especially a propylene resin) is used as the outermost layer has excellent oil resistance and heat resistance, and a styrene resin is used as the outermost layer. In this case, a product having excellent properties in terms of gloss and surface hardness can be obtained. In order to exhibit the above effects, the adhesive resin composition of the present invention can be used in a wide variety of ways, such as in the form of multilayer structures as described above. Typical uses include various trays, various containers such as cups and boxes.

Claims (1)

[Scope of Claims] 1 (A) At least one selected from the group consisting of a propylene homopolymer, a random copolymer of propylene and ethylene or an α-olefin, and a block copolymer of propylene and ethylene or an α-olefin. A kind of propylene polymer, (B) the content of vinyl acetate is 5 to 35% by weight,
and a copolymer of ethylene and vinyl acetate with a melt flow rate of 0.5 to 40 g/10 minutes, (C) an impact-resistant styrenic polymer, and (D) a block copolymer of a vinyl aromatic compound and a conjugated diene. The proportion of the propylene polymer in the composition is 1 to 20% by weight, and the proportion of the block copolymer of a vinyl aromatic compound and a conjugated diene is 1 to 25% by weight. % by weight, the composition ratio of the impact-resistant styrenic polymer is 5 to 30% by weight, and the remainder is a copolymer of ethylene and vinyl acetate.