JPS62187779A - Bondable resin composition - Google Patents

Abstract

PURPOSE:To provide the title ompsn. having excellent adhesion and blocking resistance, consisting of a propylene polymer, an ethylene/vinyl acetate copolymer, an impact-resistant styrene polymer and a hydrogenated derivative of an arom. vinyl compd./conjugated diene block copolymer. CONSTITUTION:1-20% (by weight; the same applied hereinbelow) at least one propylene polymer (A) having a comonomer content of not more than 15% and an MFR of 0.01-100g/10min selected from the group consisting of PP and block copolymers or random copolymers of propylene with ethylene or an alpha-olefin is blended with 25-93% ethylene/vinyl acetate copolymer (B) having a vinyl acetate content of 5-35% and an MFR of 0.5-40g/10min, 5-30% impact-resistant styrene coplymer (C) having an MI of 0.1-50g/10min and 1-25% hydrogenated arom. vinyl compd./conjugated diene block copolymer (D) having an arom. vinyl compd. content of 5-85%, a degree of hydrogenation of not lower than 70% and an MI of not lower than 20g/10min. The mixture is melt-kneaded at 160-300 deg.C.

Description

Detailed Description of the Invention Umbrella -- 1 No. 57 The present invention not only has good adhesion to both olefin resins (especially propylene resins) and styrene resins, but also has excellent blocking resistance. The present invention relates to an adhesive resin composition with excellent properties. More specifically, (A) a propylene homopolymer, a random copolymer of propylene and ethylene or an α-olefin, and a propylene and ethylene or α-olefin random copolymer;
- at least one propylene polymer selected from 1τ consisting of a block copolymer with an olefin, (B)
An adhesive resin composition comprising a copolymer of ethylene and vinyl acetate, (C) a #impact styrenic polymer, and (D) a hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene. It has good adhesion to both olefin resins and styrene resins, and not only has good adhesion to these molded products (e.g. films, sheets, foams), but also has #blocking properties. The purpose of this invention is to provide a resin composition with excellent properties.

Synthetic resins are widely used as packaging materials, and with the recent diversification of packaging applications, the performance of individual resins has been combined to meet all required performance. Multilayer structures are being studied and are increasingly being 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 styrene resins and the molding process. Although it is currently widely used as a variety of containers for fruits and vegetables, 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 (laminates) 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 resins and styrene resins have very poor adhesiveness to each other, so in order to obtain these multilayer structures, an adhesive layer is essential between them. Conventionally, this adhesive layer is made of a copolymer of ethylene and vinyl acetate (r
Generally, EVA shows good adhesion with olefin resins (especially ethylene polymers), but in order to obtain good adhesion with styrene resins, EVA medium is used. The content of vinyl acetate must be about 35% by weight or more, and such EVA not only has a strong vinyl acetate odor, but also has poor thermal stability and problems with extrusion stability.

In order to improve these problems, for example, a butadiene-styrene copolymer (for example, JP-A-49-33-973, JP-A-11455
-128449), styrene-isoprene block copolymer (JP-A-55-14209), ethylene-acrylic acid alkyl ester copolymer (JP-A-55-857)
No. 51), graft modified products of unsaturated carboxylic acids of block copolymers of vinyl aromatic compounds and conjugated diene compounds (for example, block copolymers of styrene and butadiene or isoprene) (JP-A-55-87551) etc. have been proposed. However, these adhesive layers
Although it exhibits fairly good adhesion with styrene resins, its adhesion with olefin resins (especially propylene resins) is insufficient. When the molding speed is high, the adhesion with propylene resin and styrene resin is not necessarily satisfactory, and the value of whichever has lower adhesion is at most 100 to 130 g/15 layers, which is not practical. Overall, this is insufficient. With this level of adhesion, various containers molded with multilayered structures obtained using these adhesive layers can be filled with, for example, food and heated at a temperature of 100 to 130°C using, for example, a microwave oven. When subjected to high-temperature heat treatment for several minutes, peeling phenomenon of the adhesive layer was observed.
Function and product value are significantly reduced.

Based on these facts, some of the inventors of the present invention have found that they do not have these drawbacks (problems), and that they can be used in both styrene resin molded products (for example, foams and sheets) and olefin resin molded products in a well-balanced manner. , practical adhesion (at least 15
0 g/15mm, preferably 200 g/1
As a result of various studies on obtaining a resin composition having (A) a propylene-based polymer (propylene-based polymer (propylene-based polymer)
Random or block copolymers based on propylene).

(B) An adhesive resin consisting of a copolymer of ethylene and vinyl acetate with a vinyl acetate content of 5 to 35% by weight, and (C) a hydrogenated product of a vinyl aromatic compound and a conjugated diene stopper block copolymer. We have previously proposed a composition that solves all of the various characteristics mentioned above (Japanese Patent Application No. 80-230).
! No. 1172).

However, in order to obtain a styrenic resin multilayer structure,
For example, when obtaining a multilayer film of two types and two layers consisting of the adhesive resin composition layer and the propylene resin layer, the adhesive resin composition and the propylene resin should have good thermal adhesion and this adhesive property. Since the resin composition itself is somewhat sticky, the blocking resistance of the adhesive resin composition layer and the propylene resin layer surface of this two-type, two-layer multilayer film is extremely poor, and the multilayer film is difficult to unwind. When thermally adhering to styrene resin, uneven tension and transportation problems occur in multilayer films.

It was found that it was not smooth and did not provide a good thermal bond.

II τ ・ -U From the following, the present invention does not have these drawbacks (problems), that is, it is suitable for both styrene resin molded products and olefin resin (especially propylene resin) molded products. Well balanced,
The object of the present invention is to obtain a resin composition that not only has the above-mentioned practical adhesive properties but also has good heat-resistant blocking properties and is free from tension unevenness and transportation troubles when thermally bonded.

81 Fortune Telling - According to the present invention, these problems are solved.

(A) At least one propylene polymer selected from the group consisting of a propylene monopolymer, a random copolymer of propylene and ethylene or an α-olefin, and a block copolymer of propylene and ethylene or an α-olefin. (B) The content of vinyl acetate is 5 to 35% by weight, and the melt flow rate (measured under conditions 4 according to JIS Ke730, hereinafter referred to as r MFRJ) is 0.
A copolymer of ethylene and vinyl acetate (hereinafter referred to as "ethylene-vinyl acetate copolymer") having a weight of 5 to 40 g 710 minutes.

(C) #! ! i! It is a composition consisting of a hydrogenated product of an Iil styrenic polymer and (D) a block copolymer of a vinyl aromatic compound and a conjugated diene, and the composition ratio of the propylene polymer in the m-acid is 1. ~20% by weight, and the composition ratio of the hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene is 1 to 25% by weight, and the composition of the impact-resistant styrenic core assembly is: - This can be solved by an adhesive resin composition in which the amount of copolymer is 5 to 30%, and the balance is ethylene-vinyl acetate copolymer. Hereinafter, the present invention will be explained in terms of SL.

(A) Propylene polymer The propylene 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 copolymer of propylene and a comonomer. selected from block copolymers of The copolymerization ratio of the comonomer is usually at least 20% by weight, especially preferably 15% by weight or less, whether it is a random copolymer or a block copolymer.Also, the number of carbon atoms in the comonomer is generally at most 1
Typical examples include ethylene, butene-1, and hexene-1,4-methylpentene-1, with ethylene being particularly preferred.The melt flow rate of the propylene polymer (measured according to JIS K8758, below) r MFRJ) is usually 0.01 to 100 g
110 minutes, preferably 0.05 to 80 g/10 minutes, particularly preferably 0.1 to 50 g/10 minutes. MFR of propylene polymer is 0.01 g/
If the time is less than 10 minutes, not only will kneadability be poor when producing the composition of the present invention, but also it will be 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 Furthermore, the vinyl acetate content (copolymerization ratio) of the ethylene-vinyl acetate copolymer used in the present invention is 5 to 3.
5% by weight, preferably 10 to 30% by weight, 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.

If an ethylene-vinyl acetate copolymer with a copolymerization ratio exceeding 35% by weight is used, the odor of vinyl acetate will be significant as described above, and thermal stability and extrusion processing stability will be lacking.

MFR of this ethylene-vinyl acetate copolymer (JIS
Measured according to K8730) is 0.5-40g/!
0 minutes, preferably 1-30 g/10 minutes,
Particularly suitable is 2 to 25 g/lG. 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. It is difficult and causes variations in adhesion. - On the other hand, if an ethylene-vinyl acetate copolymer with an MFR exceeding 40 g/10 minutes is used, 11
) The resulting composition has a high melt flow rate and poor molding stability.

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 r 5BRJ). It can also be produced by graft polymerizing a styrene monomer to a styrene monomer.Graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, and aqueous suspension polymerization, as well as combinations of these graft polymerization methods. Generally, there are methods (for example, bulk polymerization followed by aqueous suspension polymerization).
The amount of the rubber used to produce 100 parts by weight of the graft polymer (impact styrenic polymer) is 1.0 to 20 parts by weight (styrene is added to a relatively large amount of the rubber). A styrene homopolymer may be mixed into the resulting graft polymer; however, in this case, the amount of rubber used is calculated based on the mixture), and the molecular weight of the styrene bonded to the rubber as a graft chain is Usually 5
00-500.000, especially 500-300
,000 is desirable; in general, complete bonding of styrene to the rubber is rare, and there are grafts and homopolymers of styrene that are not bonded to the rubber. The homopolymer is used as is without separation. Further, the Mooney viscosity of the rubber is generally 20 to 140, particularly 30 to 120.
Preferably.

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 (411 constant according to JIS K [f870 method, hereinafter referred to as rMFIJ) of this impact-resistant styrenic polymer is not particularly specified, but is usually 0.1 to 50 g / 10 minutes. ,0.
2 to 50 g/10 min is desirable, especially 0.5
~30g/10 minutes is suitable. MFI is O
, + [If the time is less than 710 minutes, the kneading properties are poor and it is difficult to obtain a homogeneous composition. On the other hand, if the MFI is less than 50 g
/ If an impact-resistant styrenic polymer is used for more than 10 minutes, the melt flow rate of the resulting composition will be high;
Molding stability is poor.

(D) Hydrogenated product of a block copolymer of a vinyl aromatic compound and a conjugated diene Further, for producing a hydrogenated product of a block copolymer of a vinyl aromatic compound and a conjugated diene used in the present invention The block copolymers used are conjugated diene compounds such as butadiene and isoprene, and vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene.
Among them, styrene is preferred), and examples of the block form include single block copolymers, teleblock copolymers, radial teleblock copolymers, and multiblock copolymers. is,
Any of these block copolymers may be used, and the copolymerization ratio of the vinyl aromatic compound in the block copolymer is usually 5 to 85% by weight, preferably 5 to 80% by weight, particularly lθ~ 80% respect is suitable. If the copolymerization ratio of the vinyl aromatic compound is less than 5%, the adhesiveness with the styrene resin will be poor. On the other hand, if it exceeds 85%, the adhesiveness of the propylene polymer will be poor.

By highly hydrogenating the conjugated diene moiety in the above block copolymer, part or all of the two types of bonds in the main chain are saturated.

The hydrogenation ratio of the hydrogenated block copolymer of the present invention is usually 70% or more, preferably 90% or more, and particularly preferably 95% or more. If the hydrogenation rate is less than 70%, the molding of the resulting composition will lack stability.

In addition, the melt index of the hydrogenated block copolymer (according to ASTM 01238, one condition is G
(hereinafter referred to as "A,!") is 20 g/10 minutes or less, preferably 15 g/710 minutes or less.

M, 1. If a block copolymer with a weight ratio 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, and 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%, not only will the resulting composition 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%, the adhesiveness 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.

Further, the composition ratio of the hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene is 1 to 25% by weight,
2 to 25% by weight is desirable, especially 5 to 25% by weight.
Even if the proportion of the hydrogenated block copolymer in one composition is less than 1% by weight or more than 25% by weight, the adhesion to styrenic resins is particularly poor.

Furthermore, the composition ratio of fjA impact styrenic polymer is 5
-30% by weight, preferably 10-25% by weight, particularly preferably 12-25% by weight. If the composition ratio of the 1# impact-resistant styrene polymer is less than 5% by weight, the effect of improving the blocking resistance of the resulting composition is poor;
If the amount exceeds the amount by weight, the adhesion of the olefin resin and styrene resin will be poor.

From the above, it can be seen that ethylene-
The composition ratio of the vinyl acetate copolymer is 25 to 93 ton 1%, preferably 30 to 84 ton %, particularly preferably 30 to 75 ton %. In the present invention, the ethylene-vinyl acetate copolymer The reason for blending 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 or the lower limit is less than the Adhesion is not good.

(F) Composition production, molding method, etc. In producing the composition of the present invention, the above propylene polymer, ethylene-vinyl acetate copolymer, high-impact styrene polymer, and vinyl aromatic compound are conjugated. The hydrogenated block copolymer with the diene may be uniformly mixed within the above composition ratio range.
Stabilizers against heat or oxygen, lubricants, plasticizers, fillers, antistatic agents, flame retardants, pigments (colorants) and adhesive properties within the range that does not essentially lose the properties of the composition of the present invention. Additives such as imparting agents may be added.

As a mixing method, tri-blending may be performed using mixers such as a Henschel mixer, a ribbon mixer, and a tumbler, which are widely used in the field of thermoplastic resins. The mixture may be melt-kneaded using a mixer such as a mill. Among these, the latter method of melt-kneading is more preferred as a means of obtaining a more uniform composition.

From an economic point of view, mixing in a single screw extruder is preferred. Further, if necessary, the product may be passed through a screw extruder more than once.

The structure of one composition is
The process must be carried out at a temperature at which the hydrogenated products of the propylene polymer, ethylene-vinyl acetate copolymer, impact-resistant styrene polymer, and block copolymer of a vinyl aromatic compound and a conjugated diene, which are the & ingredients, melt. There is. However, these components must be carried out at temperatures at which they do not thermally decompose; therefore, the above treatments (melt cross-wiring, molding, etc.)
180-300℃ (preferably 180℃)
-250''C).

The adhesive resin composition of the present invention obtained in this way is
As mentioned above, it has good adhesion to styrene resins and olefin resins (especially propylene resins), so multilayer structures with various molded bodies made of these resins as described below can be used. It can be used as an adhesive material for manufacturing.

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 17
11J oil (vegetable oil, animal oil, 1. mineral oil) property, glossiness and high hardness of styrene resin 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 olefin resin layer or a styrene resin layer and the adhesive resin composition layer of the present invention; A multilayer structure consisting of three types and three layers in which the adhesive resin composition layer is interposed between the resin layer and the olefin resin layer and one styrene resin layer, but the total of these is three layers. A multilayer structure having the above structure and having the adhesive resin composition layer of the present invention interposed between the olefin resin layer and the styrene resin layer can be mentioned.

Typical examples of the olefin resin used to constitute this olefin resin layer include the above-mentioned propylene polymer, ethylene homopolymer (4 and ethylene and α-olefin (usually 3 to 12 carbon atoms), or Copolymers (α-
The copolymerization ratio of olefin is generally at most 20%.
, the combined proportion of the vinyl compound is usually 30% by weight or less).

Typical examples of styrene 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 50,000%) and the impact-resistant styrenic polymers mentioned above.

In producing a multilayer structure, these styrene resins and styrene resins may be used alone or as a composition of two or more types.Furthermore, the characteristics of each resin may be Compositions consisting of other thermoplastic resins and/or elastomers or various additives (e.g., various stabilizers, fillers, antistatic agents, colorants) within the range that does not essentially damage them. It may also be used as

The thickness of the adhesive resin composition layer constituting the multilayer structure is generally 1 micron or more, preferably 2 microns or more, and particularly preferably 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 following layers is not particularly limited depending on the intended use of the resulting multilayer structure. Typically, each layer has 5
It is 0 mm 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). Further, the expansion ratio of the 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 previously molded into the following molded products, and also refer to "PO
"Substrate" is a molded product obtained by pre-molding an olefin resin (e.g., film, sheet, foam), and "PS base material" is a molded product obtained by pre-molding a styrene resin (e.g.,
"Film, sheet, foam)" and "composition base material" respectively refer to molded products (eg, films, sheets) obtained by molding the adhesive resin composition of the present invention.

As a molding method, first, an extruder equipped with a T-die is used to form an adhesive resin composition, or a two-layer extruder and a two-layer co-extrusion die are used to form a styrene resin and an adhesive resin composition into PSj, Sandwich lamination method (so-called polysand method) in which the adhesive resin composition is melt-extruded between the $ material and the PO base material.Secondly, after extrusion lamination of the adhesive resin composition to the PS base material, an olefin resin is further added to this laminate. Extrusion lamination method and P02! This is a method (so-called two-layer lamination method) in which an adhesive resin composition is extrusion laminated onto an Li material, and then a styrene resin is extruded onto the laminate.

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 polysand 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 sandwich 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.

Any of the above methods must be carried out at a temperature of IH° C. or higher. If the temperature is lower than 160°C, the adhesion to the base material will be poor, which is unsatisfactory for practical use. Among these methods, there is no need to specify the upper limit temperature, but if the propylene polymer that forms the surface layer is completely melted, the appearance or commercial value will be poor, so it is recommended to set it below 200°C (
It is preferable to carry out the process at a temperature of 190° C. or lower), however, since the bonding process is usually continuous, the optimum conditions are determined by the speed line or the total thickness of the laminate.

In addition, when performing the above-mentioned lamination, the base material may be pretreated (for example, preheated) as is generally done in order to further improve the adhesion of the base material. Sandwich lamination method, which is a bonding method of
This is a bonding method in which a styrene polymer (for example, r#I# impact polystyrene) is melt-extruded using an extruder equipped with a die, and in this case, it is bonded to the molten styrene polymer layer. It goes without saying that the laminate is a final adhesive resin composition (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). do not have.

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 hot roll method, the slipperiness (blocking resistance) of the propylene polymer surface of the laminate film and the adhesive resin 1lt11 composition surface of the present invention is excellent, so that there is no local tension unevenness during lamination. It has the advantage that a multilayer structure with excellent appearance and no wrinkles can be obtained.

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.

A multilayer structure made in this way has not only good heat resistance but also excellent oil resistance when its surface layer is an olefin resin layer (especially a propylene resin layer), and also has a surface When the layer is made of styrene resin, it is characterized by not only high gloss but also excellent hardness.

The present invention will now be explained in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, the adhesive strength was measured using a Tensilon type tensile tester, and the peeling speed was 1001111.
The resistance value was determined by peeling in a direction of 180 degrees at a speed of 180°/min.

Further, the evaluation of the pro-7 kinging resistance of the coextruded film was carried out by measuring the coefficient of friction (ASTM 01894 method) between the surface of the polypropylene layer and the surface of the adhesive layer of the coextruded film.

In the Examples and Comparative Examples, the propylene polymer was an ethylene-propylene random copolymer with an ethylene content of 2.0% (MFR3, 5g/1
0 minutes, hereinafter referred to as rPPJ). In addition, as an ethylene-vinyl acetate copolymer, the vinyl acetate content is 2
0.5fi Q% ethylene-vinyl acetate copolymer (MFR3,8g/10min, hereinafter referred to as rEVAJ)
was used. Furthermore, as a hydrogenated product of a block copolymer of styrene and conjugated diene, a hydrogenated styrene-butadiene-styrene block copolymer having a hydrogenation rate of 99% or more and a styrene content of 29% by weight. (MFR1,
8 g/10 minutes, hereinafter referred to as "hydrogenated 5BSJ".In addition, as an impact-resistant styrenic polymer, 34.3 parts by weight of styrene was added to 5.7 parts by weight of styrene-butadiene copolymer rubber. Graft B (combination (NFR 3, 2 g/10 min, hereinafter referred to as "former PSJ") obtained by graft polymerization was used.

Examples 1 to 8, Comparative Examples 1 to 4 PP, EVA, hydrogenated SBS, and old PS whose compositions are shown in Table 1 were triblended 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) has an MFR of 9.2 g/10
The thickness of the propylene homopolymer (A) ((B
)/(A) ) is 20 microns and 150 microns multilayer T
A coextruded film was created using a die-filming 9-position machine. (A) layer and (B) layer in each coextruded film obtained
) The adhesion strength between the layers was measured. Furthermore, the coefficient of friction between the surface of the propylene homopolymer (pp) layer of the coextruded film and the adhesive resin composition was measured. The results are shown in Table 1.

Each coextruded film was then heated to a thickness of 0.2 using a heated roll set at the temperature shown in Table 1.
Styrenic resin sheet (PSS) or styrenic resin foam of the same thickness (psp, foaming ratio approximately 10)
A multilayer structure was created in which a styrene resin (PS), an adhesive resin composition, and a propylene homopolymer were sequentially laminated. 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.

(Left below) From the results of the above Examples and Comparative Examples, it is clear that the adhesive resin composition obtained by the present invention has good adhesion to both olefin resins (particularly propylene resins) and styrene resins. Furthermore, it is clear that the laminate consisting of the adhesive resin composition and the olefin resin has good interlayer adhesion and is also extremely excellent in blocking resistance. be. Furthermore, in the case of the present invention, the outermost layer of the resulting multilayer structure is composed of an olefin polymer with excellent oil resistance and heat resistance. For example, curry,
It is clear that it can be used in many ways as a packaging container for foods such as tempura and fried noodles.

The adhesive resin composition t3 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 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.

The adhesive resin composition of the present invention can be used in a wide variety of ways, such as in the form of the multilayer structure described above, in order to exhibit the above effects. Typical uses include various trays (particularly trays for oil-based foods such as curry, tempura, and yakisoba), and various containers such as cups and joints.

Claims (1)

[Scope of Claims] (A) At least one member 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. propylene-based polymer, the content of (B) vinyl acetate is 5 to 35% by weight, and the melt flow rate is 0.5 to 40 g
/10 minutes; (C) an impact-resistant styrenic polymer; and (D) a hydrogenated product of a block copolymer of a vinyl aromatic compound and a conjugated diene. The composition ratio of the propylene polymer in the composition is 1 to 20% by weight, and the composition ratio of the hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene is 1 to 25% by weight. % by weight, and 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.