JP2016107444A - Laminate, formed body, formed cup, and container for beverage product - Google Patents

Abstract

A barrier resin layer and a polystyrene-based resin layer imparting rigidity are laminated and integrated with good interlayer adhesion, and after being subjected to a heat-stretching process such as cup molding and further used in a high temperature state. Provides a laminate capable of maintaining good interlayer adhesion. A laminate comprising an EVOH resin or polyamide resin layer (α), an adhesive layer, and a resin layer (β) such as polystyrene resin. The adhesive layer comprises the following components (a) to (d), 45 to 85% by weight of component (a), 5 to 30% by weight of component (b), and component (c): 5 with respect to the total amount. It consists of an adhesive resin composition containing -30 wt% and component (d): 5-20 wt%. Component (a): Metallocene-catalyzed polyethylene resin component (b) having a density of 0.890 to 0.920 g / cm 3 (b): Alicyclic saturated hydrocarbon resin component (c): Acid-modified polyethylene resin component (d): Aromatic Hydrogenated vinyl vinyl / conjugated diene block copolymer [selection] None

Description

  In the present invention, a barrier resin layer made of saponified ethylene-vinyl acetate copolymer (EVOH resin) or polyamide resin and a layer imparting rigidity such as polystyrene resin are laminated and integrated with good interlayer adhesion. Thus, the present invention relates to a laminate capable of obtaining good adhesion even after undergoing a heating and stretching step such as cup molding, and further maintaining good interlayer adhesion even when used in a high temperature state. The present invention also relates to a molded body, a molded cup and a beverage product container using the laminate.

  Polyolefin resins, which are copolymers with polyethylene resins, polypropylene resins, and other olefin monomers, have excellent properties in moldability, cost, hygiene, heat sealability, etc. It is used as a constituent material. In particular, from the viewpoint of heat sealability and hygiene, it is often used as the innermost layer, that is, a layer in contact with food. Moreover, in order to keep freshness, a color, and a taste long during the preservation | save period of a foodstuff, providing the oxygen shielding function to a packaging material is also performed widely. For example, polyamide resin, saponified ethylene-vinyl acetate copolymer resin (EVOH resin), or the like is used as the oxygen barrier layer. Furthermore, in the case where rigidity is required for the packaging material, such as in the case of packaging materials for containers, and in applications where thermoformability and stretchability are required, such as cups and trays, polystyrene resins and the like are used.

  For the purpose of imparting various performances as described above to one packaging material, various materials are laminated. There are various lamination methods such as a co-extrusion method, dry lamination, wet lamination, extrusion lamination, etc., but it is the co-extrusion method that can efficiently laminate polystyrene resin, EVOH resin, and polyolefin resin. However, in order to laminate these resins by the coextrusion method, an adhesive resin for adhering the respective layers is essential. Thus, various adhesive resins have been developed and used for beverage cups, lunch boxes, containers such as margarine and butter, and dairy products such as yogurt.

  In application to these food containers, the adhesive resin used for adhesion between layers not only shows good interlayer adhesion when each layer is laminated, but also reheats the produced laminate according to its use. Then, after passing through the stretching process when shaping into a desired shape such as a cup, further, processing, storage or use under high temperature conditions such as high temperature sterilization, microwave heating, storage in a heat insulation case, etc. In some cases, it is required to maintain good interlayer adhesion.

  Conventional adhesive resins used for food containers include, for example, carboxylic acid-modified ethylene / α-olefin copolymers, ethylene polymers, tackifiers, and block copolymers of vinyl aromatic compounds and conjugated diene compounds. An adhesive resin composition comprising a polymer hydrogenated product has been proposed (Patent Document 1). Also, an adhesive resin composition having a specific broad melting behavior has been proposed, comprising an acid-modified ethylene polymer, a tackifier, and a hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene compound. (Patent Document 2).

JP-A-10-264323 JP 2000-086840 A

  As a result of detailed investigations by the present inventors, the adhesive resin compositions of Patent Document 1 and Patent Document 2 can obtain an interlayer adhesive strength that causes no problem when used at room temperature. It was found that the adhesive strength in the temperature region near 100 ° C., which is required in applications such as hot water extraction containers, in particular after being formed into shapes such as food containers and beverage containers, is not sufficient. .

  The present invention has been made in view of the above-described prior art, and the problem is that a barrier resin layer such as an EVOH resin or a polyamide resin and a polystyrene resin layer that imparts rigidity have good interlayer adhesion. And a laminate capable of obtaining good adhesion even after a heat stretching process such as cup molding and maintaining good interlayer adhesion even in use at a high temperature, and this lamination It is providing the molded object obtained by using a body, a shaping | molding cup, and the container for drinks.

  As a result of intensive studies by the present inventors, a resin layer selected from saponified ethylene-vinyl acetate copolymer and polyamide resin, and a layer imparting rigidity such as polystyrene resin, an adhesive resin having a specific composition It has been found that a laminate formed by laminating and integrating with a composition can solve the above problems. That is, the gist of the present invention is as follows [1] to [10].

[1] Resin layer (α) selected from saponified ethylene-vinyl acetate copolymer and polyamide resin, adhesive layer, polystyrene resin, polyester resin, polyamide resin, polycarbonate resin, and polyvinyl chloride A laminate including a resin layer (β) selected from a resin, wherein the adhesive layer includes the following component (a), component (b), component (c), and component (d): ) To (d), 45 to 85% by weight of component (a), 5 to 30% by weight of component (b), 5 to 30% by weight of component (c), and 5 of component (d). A laminate comprising an adhesive resin composition containing -20% by weight.
Component (a): Polyethylene resin component polymerized from a metallocene catalyst and having a density of 0.890 to 0.920 g / cm ³ (b): Alicyclic saturated hydrocarbon resin component (c): Acid-modified polyethylene resin component (d): hydrogenated block copolymer having an aromatic vinyl block and a conjugated diene block

[2] The laminate according to [1], wherein the content of the aromatic vinyl block of the component (d) is 20 to 65% by weight.

[3] The laminate according to [1] or [2], wherein the component (d) has a melt viscosity of 100 to 2,000 Pa · s at a temperature of 230 ° C. and a shear rate of 60 s ⁻¹ .

[4] The laminate according to [1] to [3], wherein the softening point of the component (b) is 100 to 180 ° C.

[5] The melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg of the component (a) is 0.1 to 10.0 g / 10 min, according to any one of [1] to [4]. Laminated body.

[6] The Vicat softening point (JIS K7206 (1999)) of the adhesive resin composition is 70 to 100 ° C, and the melt flow rate (MFR) at 190 ° C and a load of 2.16 kg is 0.1 to 10. The laminate according to any one of [1] to [5], which is 0 g / 10 minutes.

[7] A molded body obtained by thermoforming the laminate according to any one of [1] to [6].

[8] The laminate according to any one of [1] to [6] is thermoformed, has the resin layer (α) on the inner layer side, and has the resin layer (β) on the outer layer side. Molded cup.

[9] A beverage container comprising the laminate according to any one of [1] to [6].

[10] The beverage container according to [9], having the resin layer (α) on the inner layer side and the resin layer (β) on the outer layer side.

  According to the present invention, a barrier resin layer such as EVOH resin or polyamide-based resin and a layer imparting rigidity such as polystyrene-based resin are laminated and integrated with good interlayer adhesion, and a heat stretching process such as cup molding. Thus, it is possible to provide a laminate capable of obtaining good adhesion even after passing through and maintaining good interlayer adhesion even when used in a high temperature state. Further, according to the present invention, a molded body excellent in interlayer adhesion that can sufficiently withstand use in a wide temperature range from low temperature to near 100 ° C., a molded cup, and a molded cup, A beverage container is provided.

  Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist. is not. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.

[Laminate]
The laminate of the present invention includes a resin layer (α) selected from saponified ethylene-vinyl acetate copolymer and polyamide resin (hereinafter sometimes referred to simply as “resin layer (α)”), an adhesive layer, In addition, a resin layer (β) selected from polystyrene-based resins, polyester-based resins, polyamide-based resins, polycarbonate-based resins, and polyvinyl chloride-based resins (hereinafter sometimes simply referred to as “resin layer (β)”). The adhesive layer includes the following component (a), component (b), component (c), and component (d), and the total amount of components (a) to (d): An adhesive resin composition comprising 45 to 85% by weight of component (a), 5 to 30% by weight of component (b), 5 to 30% by weight of component (c) and 5 to 20% by weight of component (d). It is characterized by comprising.
Component (a): Polyethylene resin component polymerized from a metallocene catalyst and having a density of 0.890 to 0.920 g / cm ³ (b): Alicyclic saturated hydrocarbon resin component (c): Acid-modified polyethylene resin component (d): hydrogenated block copolymer having an aromatic vinyl block and a conjugated diene block

[Adhesive resin composition]
First, an adhesive resin composition (hereinafter sometimes referred to as “adhesive resin composition of the present invention”) that forms the adhesive layer of the laminate of the present invention will be described.

The adhesive resin composition of the present invention includes the following components (a) to (d) at a predetermined ratio.
Component (a): Polyethylene resin component polymerized from a metallocene catalyst and having a density of 0.890 to 0.920 g / cm ³ (b): Alicyclic saturated hydrocarbon resin component (c): Acid-modified polyethylene resin component (d): hydrogenated block copolymer having an aromatic vinyl block and a conjugated diene block

<Component (a)>
Component (a) is a polyethylene resin having a density of 0.890 to 0.920 g / cm ³ polymerized from a metallocene catalyst, and functions to adjust moldability (fluidity) and flexibility as a matrix resin for the adhesive layer. Take on.

  The polyethylene-based resin of component (a) is an ethylene homopolymer or a block or random copolymer of ethylene and another copolymer monomer. Examples of the copolymerization monomer include α-olefin, vinyl ester, unsaturated carboxylic acid or ester thereof. Here, the α-olefin is usually an α-olefin not containing a cyclic molecule having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc., each consisting of a single or a mixture of two or more. Examples of vinyl esters include vinyl acetate and vinyl butyrate. Examples of unsaturated carboxylic acids or esters thereof include acrylic acid, methacrylic acid, methyl acrylate, and ethyl acrylate.

  Specific examples of the polyethylene resin of component (a) include low density polyethylene (usually referred to as LDPE), linear low density polyethylene (usually referred to as LLDPE), and very low density polyethylene (usually referred to as VLDPE). Low crystalline ethylene / butene-1 random copolymer (usually called EBM), ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, etc. Among these, linear low density polyethylene is preferable, and linear low density polyethylene is more preferable.

The polyethylene resin used as the component (a) in the present invention has a density of 0.890 to 0.920 g / cm ³ . When the density of the component (a) is 0.890 g / cm ³ or more, high-temperature adhesiveness between layers in the laminate of the present invention and a molded product obtained by thermoforming the laminate is improved. From this viewpoint, the density of the polyethylene resin as the component (a) is preferably 0.895 g / cm ³ or more, and particularly preferably 0.900 g / cm ³ or more. On the other hand, when the density of the component (a) is 0.920 g / cm ³ or less, the room temperature adhesiveness between layers is improved. From this viewpoint, the density of the polyethylene-based resin as the component (a) is preferably 0.916 g / cm ³ or less, particularly preferably 0.912 g / cm ³ or less.
Here, the density of the polyethylene resin is a value measured by an underwater substitution method according to JIS K7112 (1999).

Moreover, the polyethylene-type resin of a component (a) is manufactured using the metallocene catalyst.
In other words, polyethylene resins are generally produced using Ziegler-Natta catalysts, chromium catalysts, vanadium catalysts, metallocene catalysts, etc. Among these, those produced using metallocene catalysts have a molecular weight distribution. Therefore, stable adhesiveness can be exhibited in a wide temperature range from room temperature to high temperature.

Although there is no restriction | limiting in particular about the melt flow rate (MFR) of the polyethylene-type resin of a component (a), It is preferable in order to become moderate fluidity | liquidity and to shape | mold easily that it is 0.1-10.0 g / 10min. From this viewpoint, the MFR of the polyethylene resin is more preferably 0.3 g / 10 min or more, further preferably 0.5 g / 10 min or more, and on the other hand, 8.0 g / 10 min or less. Is more preferably 6.0 g / 10 min or less, and particularly preferably 4.0 g / 10 min or less.
Here, the MFR of the polyethylene resin is a value measured at a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210-1 (2014).

  The adhesive resin composition of the present invention may contain only one kind of the above-mentioned polyethylene-based resin as the component (a). 2 or more of different things such as MFR may be included.

  The adhesive resin composition of the present invention comprises, as component (a), the above-mentioned polyethylene-based resin, a total of 100 components (a) and components (b), (c), and (d) described later. It contains 45 to 85% by weight with respect to% by weight. When the content of the component (a) in the adhesive resin composition of the present invention is 45% by weight or more, the effect of adjusting the moldability (fluidity) and flexibility as a matrix resin by the component (a) is sufficient. And high temperature adhesion can be improved. From this viewpoint, the content of the component (a) in the adhesive resin composition of the present invention is preferably 50% by weight or more, and more preferably 55% by weight or more. On the other hand, when the content of the component (a) in the adhesive resin composition of the present invention is 85% by weight or less, a suitable content of other components is relatively secured and good in a wide temperature range. Excellent adhesion can be obtained. From this viewpoint, the content of the component (a) in the adhesive resin composition of the present invention is preferably 80% by weight or less, and more preferably 75% by weight or less.

<Component (b)>
Component (b) is an alicyclic saturated hydrocarbon resin.
The alicyclic saturated hydrocarbon resin is a saturated hydrocarbon having a main chain composed of hydrocarbon and an alicyclic structure. Specifically, a hydrogenated petroleum resin obtained by hydrogenating an aromatic petroleum resin, an aromatic type Examples thereof include a resin obtained by hydrogenating a petroleum resin containing a compound, a resin obtained by hydrogenating an alicyclic hydrocarbon resin having an unsaturated bond, and the like. By this hydrogenation, the aromatic ring is converted to an alicyclic saturated structure.

  The alicyclic saturated hydrocarbon resin of the component (b) has good compatibility with the component (a) and has good compatibility with the component (d) described later. By adhering to component (a) or component (d), it is possible to impart tackiness and develop adhesiveness to the resin layer (β). In addition, the alicyclic saturated hydrocarbon resin is an aliphatic resin used as a tackifier in a normal adhesive resin composition in that it is difficult to bleed out from the adhesive resin composition and easy to obtain tackiness. It is preferable compared to petroleum resins and aromatic petroleum resins.

  Examples of alicyclic saturated hydrocarbon resins include hydrogenated terpene resins (Clearon (registered trademark) P, M, and K series manufactured by Yashara Chemical Co., Ltd.), hydrogenated rosins, and hydrogenated rosin ester resins (Rika Fine Co., Ltd.). Tec Foral (registered trademark) AX, Foral 105, Arakawa Chemical Industry Co., Ltd. Pencel (registered trademark) A, Arakawa Chemical Industry Co., Ltd. ester gum (registered trademark) H, Arakawa Chemical Industry Co., Ltd. super ester (Registered trademark A series), disproportionated rosin and disproportionated rosin ester resin (Pine Crystal (registered trademark) series manufactured by Arakawa Chemical Industries, Ltd.), pentene, isoprene, piperine produced by pyrolysis of petroleum naphtha Hydrogenated dicyclopentadiene, which is a hydrogenated resin of C5 petroleum resin obtained by copolymerizing C5 fractions such as 1,3-pentadiene Fat (Donex Co., Ltd. Escorez (registered trademark) 5300, 5400 series, Eastman Chemical Japan Co., Ltd. Eastotac (registered trademark) H series), partially hydrogenated aromatic modified dicyclopentadiene resin (Tonex Co., Ltd.) Escoretz (registered trademark) 5600 series), C9 petroleum resin obtained by copolymerizing C9 fraction such as indene, vinyltoluene, α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha was hydrogenated. Resin (Arcon (registered trademark) P and M series manufactured by Arakawa Chemical Industries, Ltd.), and a resin hydrogenated from the above-described copolymer petroleum resin of C5 fraction and C9 fraction (Imabe (registered trademark) manufactured by Idemitsu Kosan Co., Ltd.) ) Series). These alicyclic saturated hydrocarbon resins may be used alone or in combination of two or more.

  The alicyclic saturated hydrocarbon resin preferably has a softening point of 100 ° C or higher, more preferably 115 ° C or higher, particularly 125 ° C or higher, as measured by JIS K6823 (ring and ball method). Preferably, it is preferably 180 ° C. or lower, more preferably 175 ° C. or lower, still more preferably 170 ° C. or lower, and particularly preferably 165 ° C. or lower. There exists a tendency for high temperature adhesive strength and a moldability to become it more favorable that a softening point is more than the said lower limit. On the other hand, when the softening point is not more than the above upper limit value, the moldability tends to be good.

  The adhesive resin composition of the present invention comprises the above-mentioned alicyclic saturated hydrocarbon resin as the component (b), the component (a), the component (b), the component (c) and the component (d) described later 5 to 30% by weight with respect to 100% by weight in total. When the content of the component (b) in the adhesive resin composition of the present invention is 5% by weight or more, the effect of the adhesive expression on the resin layer (β) by the component (b) can be sufficiently obtained. Can do. From this viewpoint, the content of the component (b) in the adhesive resin composition of the present invention is preferably 10% by weight or more, and more preferably 15% by weight or more. On the other hand, when the content of the component (b) in the adhesive resin composition of the present invention is 30% by weight or less, a suitable content of other components is relatively ensured and good in a wide temperature range. Excellent adhesion can be obtained. From this viewpoint, the content of the component (b) in the adhesive resin composition of the present invention is preferably 28% by weight or less, and more preferably 26% by weight or less.

<Component (c)>
The component (c) acid-modified polyethylene resin is obtained by acid-modifying a polyethylene resin with an unsaturated carboxylic acid and / or a derivative thereof, and is selected from ethylene-vinyl acetate copolymer saponified products and polyamide resins. It is a component that improves the adhesion with the resin layer (α).

  The polyethylene resin used as the raw material for the acid-modified polyethylene is ethylene homopolymer or ethylene / α which is a copolymer of ethylene with vinyl ester such as α-olefin and vinyl acetate, unsaturated carboxylic acid ester and the like. -Ethylene copolymers, such as an olefin copolymer, an ethylene / vinyl ester copolymer, and an ethylene / unsaturated carboxylic acid ester copolymer. The α-olefin constituting the ethylene / α-olefin copolymer is usually an α-olefin not containing a cyclic molecule having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl. -1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc., each consisting of a single compound or a mixture of two or more. Examples of the ethylene / vinyl ester copolymer include an ethylene / vinyl acetate copolymer. Examples of the ethylene / unsaturated carboxylic acid ester copolymer include an ethylene / acrylic acid ester copolymer and an ethylene / methacrylic acid ester copolymer. Furthermore, these polyethylene resins can be used in combination of two or more.

  Specific examples of the polyethylene resin used as the raw material for the acid-modified polyethylene include, for example, low density polyethylene (LDPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), ultra Low density polyethylene (VLDPE), low crystalline ethylene / butene-1 random copolymer (EBM), ethylene / propylene copolymer, ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer, etc. Can be mentioned.

  On the other hand, the acid component used for acid modification is an unsaturated carboxylic acid and / or a derivative thereof, such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid. Unsaturated carboxylic acids such as R (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), or derivatives of these unsaturated carboxylic acids, such as acid halides, amides, imides , Anhydrides, esters and the like. More specifically, there may be mentioned maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monometer maleate, dimethyl maleate, glycidyl maleate, etc. Among these, anhydrides of unsaturated carboxylic acids are preferred and anhydrous Maleic acid is most preferred. These may use only 1 type and may mix and use 2 or more types.

  In order to produce the acid-modified polyethylene resin of component (c), various conventionally known methods can be employed. For example, the above-mentioned polyethylene resin, unsaturated carboxylic acid and / or derivative thereof, and radical generator are mixed in advance and melted with an extruder and graft copolymerized, or radical is generated by dissolving the polyethylene resin in a solvent. Examples thereof include a method in which an agent and an unsaturated carboxylic acid and / or a derivative thereof are added to perform graft copolymerization. In any case, in order to efficiently graft copolymerize the unsaturated carboxylic acid and / or derivative thereof, it is preferable to carry out the reaction in the presence of a radical generator. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The amount of the radical generator used is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyethylene resin.

  As radical generators, organic peroxides, organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne -3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octoate, t-butylperpi Valate, cumyl perpivalate and t-butyl Pell diethyl acetate, other azo compounds, for example, can be mentioned azobisisobutyronitrile, dimethyl azoisobutyrate, and the like. Among these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t It is preferable to use dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxydiisopropyl) benzene.

Such an acid-modified polyethylene resin of component (c) preferably has an acid modification amount of 0.01 to 2.0% by weight. When the acid modification amount is 0.01% by weight or more, the effect of improving the adhesion to the resin layer (α) by acid modification can be sufficiently obtained, and when it is 2.0% by weight or less, the resin layer (β) Adhesiveness at the interface with the resin becomes appropriate, and the appearance of the resulting laminate can be made better. From this viewpoint, the acid modification amount of the acid-modified polyethylene resin is more preferably 0.05% by weight or more, and further preferably 0.1% by weight or more. Moreover, it is more preferable that it is 1.5 weight% or less, and it is still more preferable that it is 1.0 weight% or less. The amount of acid modification is a value determined by FT-IR as an area% of the peak area of unsaturated carboxylic acid and / or its derivative with respect to the total absorption peak area of 700 to 4000 cm ⁻¹ .

  Although there is no restriction | limiting in particular about the melt flow rate (MFR) of the acid-modified polyethylene resin of a component (c), it is 0 as a value measured by the temperature of 190 degreeC and the load of 2.16 kg according to JISK7210-1 (2014). It is preferable that it is 1-10.0g / 10min. The MFR of the acid-modified polyethylene resin is preferably 0.1 g / 10 min or more from the viewpoint of fluidity. In this respect, the MFR of the acid-modified polyethylene resin is more preferably 0.2 g / 10 min or more, and further preferably 0.3 g / 10 min or more. On the other hand, when the MFR of the acid-modified polyethylene resin is 10.0 g / 10 min or less, the dispersion with the component (a) tends to be better. In this respect, the MFR of the acid-modified polyethylene resin is more preferably 8.0 g / 10 minutes or less, and still more preferably 6.0 g / 10 minutes or less.

  The adhesive resin composition of the present invention may contain only one kind of the above-mentioned acid-modified polyethylene resin as the component (c), a copolymer monomer composition of the polyethylene resin before acid modification, It may contain two or more different ones such as acid used for acid modification, acid modification amount, MFR and the like.

  The adhesive resin composition of the present invention comprises the above acid-modified polyethylene resin as the component (c), the component (a) and the component (b), the component (c), and the component (d) described later. 5 to 30% by weight with respect to 100% by weight in total. When the content of the component (c) in the adhesive resin composition of the present invention is 5% by weight or more, the effect of improving the adhesion with the resin layer (α) by the component (c) can be sufficiently obtained. it can. From this viewpoint, the content of the component (c) in the adhesive resin composition of the present invention is preferably 6% by weight or more, and more preferably 7% by weight or more. On the other hand, when the content of the component (c) in the adhesive resin composition of the present invention is 30% by weight or less, the appearance at the interface with the resin layer (β) tends to be good, Relatively suitable content of other components can be ensured and good adhesiveness in a wide temperature range can be obtained. From this viewpoint, the content of the component (c) in the adhesive resin composition of the present invention is preferably 25% by weight or less, and more preferably 20% by weight or less.

<Component (d)>
A hydrogenated block copolymer having an aromatic vinyl block and a conjugated diene block as component (d) (hereinafter sometimes referred to as “hydrogenated block copolymer”) is used as a polystyrene resin or the like. It is a component that has high adhesiveness, has high affinity with the above-mentioned component (b) at room temperature, and has a function of improving room temperature adhesion with a resin layer (β) such as polystyrene resin.

  When the block copolymer of component (d) is an aromatic vinyl block made of a polymer of a vinyl aromatic compound and block B is a conjugated diene block made of a polymer of a conjugated diene compound, AB , A-B-A, B-A-B-A, A-B-A-B-A, B-A-B-A-B, and the like. The block copolymer preferably has an ABA structure.

  As a vinyl aromatic compound which comprises the aromatic vinyl block A, 1 type (s) or 2 or more types, such as styrene, (alpha) -methylstyrene, vinyl toluene, are mentioned, for example. Of these, styrene is preferably used.

  On the other hand, examples of the conjugated diene compound constituting the conjugated diene block B include one or more of butadiene, isoprene, 1,3-pentadiene, and the like. Of these, butadiene, isoprene and combinations thereof are preferred.

  The content of the aromatic vinyl block A is preferably 20 to 65% by weight, and more preferably 25 to 60% by weight. That is, the content of the conjugated diene block B is preferably 80 to 35% by weight, and more preferably 75 to 40% by weight. In the said range, it exists in the tendency for adhesiveness to become favorable, so that there is much content of the aromatic vinyl block A, and it exists in the tendency for an external appearance to become favorable, so that there is little.

  The hydrogenation rate of the conjugated diene block B of the hydrogenated block copolymer of component (d) is generally 50% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 95%. That's it. A higher hydrogenation rate is particularly preferable because thermal stability is improved.

The hydrogenated block copolymer of component (d) has a melt viscosity of 100 to 2,000 Pa · s measured at a temperature of 230 ° C. and a shear rate of 60 s ⁻¹ with the component (a) that is a matrix resin. This is preferable because of good dispersion. In this respect, the melt viscosity of the hydrogenated block copolymer is more preferably 200 Pa · s or more, further preferably 400 Pa · s or more, and more preferably 1,900 Pa · s or less. Preferably, it is 1,800 Pa · s or less. The melt viscosity can be measured using Toyo Seiki Seisakusho Co., Ltd., product name Capillograph, Model 1D (barrel diameter: 9.55 mm, barrel length: 350 mm, nozzle diameter: 1 mm, nozzle length: 10 mm).

  The melt flow rate (MFR) of the hydrogenated block copolymer of component (d) is not particularly limited, but the MFR measured at a temperature of 230 ° C. and a load of 2.16 kg is 0.1% according to ISO-1133. It is preferable from the viewpoint of appearance that it is ˜10.0 g / 10 min. In this respect, the MFR of the hydrogenated block copolymer is more preferably 0.2 g / 10 min or more, further preferably 0.4 g / 10 min or more, and 8.0 g / 10 min or less. More preferably, it is more preferably 6.0 g / 10 min or less.

  The adhesive resin composition of the present invention comprises the above-mentioned hydrogenated block copolymer as the component (d), and the total of the components (a), (b) and (c) and the component (d). 5 to 20% by weight with respect to 100% by weight. When the content of the component (d) in the adhesive resin composition of the present invention is 5% by weight or more, the effect of improving the adhesiveness with the polystyrene resin layer (β) by the component (d) is sufficiently obtained. be able to. From this viewpoint, the content of the component (d) in the adhesive resin composition of the present invention is preferably 6% by weight or more, and more preferably 7% by weight or more. On the other hand, when the content of the component (d) in the adhesive resin composition of the present invention is 20% by weight or less, a suitable content of other components is relatively secured and good in a wide temperature range. Excellent adhesion can be obtained. From this viewpoint, the content of the component (d) in the adhesive resin composition of the invention is preferably 18% by weight or less, and more preferably 16% by weight or less.

<Other ingredients>
The adhesive resin composition of the present invention contains various additives generally blended in the resin composition in addition to the above component (a), component (b), component (c) and component (d). You may contain in the range which does not impair the objective of invention. Such additives include antioxidants, heat stabilizers, weathering stabilizers, anti-blocking agents, slip agents, antistatic agents, flame retardants, neutralizers for catalyst residues, pigments, dyes, inorganic and / or organic A filler etc. are mentioned.

<Method for producing adhesive resin composition>
In the adhesive resin composition of the present invention, the above-mentioned components (a) to (d) and other components used as necessary may be used in various known methods such as a tumbler blender, a V blender, a ribbon blender, a Henschel mixer, etc. , And after mixing, the mixture can be melt-kneaded with a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, etc., and granulated or pulverized.

<Physical properties of adhesive resin composition>
The adhesive resin composition of the present invention preferably has a Vicat softening point of 70 to 100 ° C. as measured by JIS K7206 (1999). In addition, the specific measuring method of Vicat softening point is shown in the Example mentioned later.

  When the Vicat softening point of the adhesive resin composition is 70 ° C. or higher, the heat resistance of the adhesive resin composition itself is good, and the high-temperature adhesiveness tends to be good. In this respect, the Vicat softening point is more preferably 75 ° C. or higher. Moreover, it exists in the tendency for cup moldability to become favorable because the Vicat softening point of an adhesive resin composition is 100 degrees C or less. In this respect, the Vicat softening point is more preferably 95 ° C. or lower.

  Moreover, according to JIS7210-1 (2014) of an adhesive resin composition, it is preferable that the melt flow rate (MFR) measured by 190 degreeC and a load 2.16kg is 0.1-10.0 g / 10min. . When the MFR is 1.0 g / 10 min or more, the multilayer sheet formability tends to be good. From this viewpoint, the MFR is more preferably 0.2 g / 10 min or more, and further preferably 0.4 g / 10 min or more. Moreover, it exists in the tendency for the external appearance when it is set as a laminated sheet and a shaping | molding cup to become favorable because MFR of an adhesive resin composition is 10.0 g / 10min or less. From this viewpoint, the MFR is more preferably 7.0 g / 10 min or less, and further preferably 5.0 g / 10 min or less.

[Resin layer (α)]
In the laminate of the present invention, the resin layer (α) selected from the saponified ethylene-vinyl acetate copolymer and the polyamide-based resin is a layer that functions as a gas barrier layer.

<Saponified ethylene-vinyl acetate copolymer>
The ethylene-vinyl acetate copolymer saponified product (EVOH resin) used for the resin layer (α) is preferably an ethylene-vinyl acetate copolymer having an ethylene content of preferably 15 to 60 mol%, more preferably 25 to 50 mol%. A saponified product is preferably used so that the degree of saponification is 50% or more, preferably 60% or more. When the ethylene content is less than the above lower limit, it tends to be thermally decomposed and difficult to be melt-molded, it is inferior in stretchability, and it tends to absorb water and swell, resulting in poor water resistance. On the other hand, when the ethylene content exceeds the above upper limit, the gas barrier property tends to decrease. Moreover, there exists a tendency for gas barrier property to fall that a saponification degree is less than the said minimum.

<Polyamide resin>
Polyamide resins used for the resin layer (α) include hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1, Aliphatic, alicyclic, aromatic and other diamines such as 4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, adipic acid, suberic acid, sebacic acid , Polyamide resins obtained by polycondensation with aliphatic, alicyclic and aromatic dicarboxylic acids such as cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid, and aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanecarboxylic acid Polyamide resin obtained by acid condensation, ε-caprolactam, ω-laurolacta Polyamide resin obtained from lactams etc., or can be exemplified mixtures of copolyamide resin composed of these components. Specific examples include nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, and the like. Among these, it is preferable to use nylon 6 and nylon 66 which are excellent in melting point, rigidity and the like. The molecular weight is not particularly limited, but a polyamide resin having a relative viscosity ηr (measured in JIS K6810, 98% sulfuric acid) of 0.5 or more is usually used. preferable.

[Resin layer (β)]
The resin layer (β) selected from polystyrene-based resins, polyester-based resins, polyamide-based resins, polycarbonate-based resins, and polyvinyl chloride-based resins is a layer for imparting rigidity and the like to the laminate of the present invention.

<Polystyrene resin>
The polystyrene resin used for the resin layer (β) is a styrene homopolymer, a copolymer of styrene and acrylonitrile, methyl methacrylate, or the like, or a polystyrene resin mainly composed of styrene such as a rubber-modified product thereof. Is mentioned. Specific examples include polystyrene resin, impact-resistant polystyrene resin (rubber-containing polystyrene resin), styrene / acrylonitrile resin (AS resin), acrylonitrile / styrene / butadiene copolymer resin (ABS resin), and the like. In the resin layer (β), only one kind of these resins may be used, or two or more kinds may be used.

  The polystyrene resin used for the resin layer (β) has a melt flow rate (MFR) measured at 200 ° C. and a load of 5 kg in accordance with ISO-1133, 0.1 to 50 g / 10 min, particularly 1 to 20 g / 10 min. A range is preferable. When the MFR is out of the above range, the moldability tends to decrease.

<Polyester resin>
Examples of polyester resins used for the resin layer (β) include terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, aromatic dicarboxylic acids such as naphthalene-1,4- or 2,6-dicarboxylic acid, and oxalic acid. Acid components of dicarboxylic acids such as aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and undecadicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid, ethylene glycol, propylene glycol, 1, 4 -An aliphatic glycol such as butanediol and neopentyl glycol, an alicyclic glycol such as cyclohexanedimethanol, and a glycol component such as an aromatic dihydroxy compound such as bisphenol A. Polyethylene terephthalate (PET) Combined PET, polybutylene terephthale Preparative (PBT), polyethylene naphthalate (PEN), can be exemplified polycyclohexylenedimethylene thin terephthalate (PCT) and the like. Among these, polyethylene terephthalate (PET) is particularly preferable, and is usually a thermoplastic polyester resin in which 80 mol% or more of the dicarboxylic acid component is terephthalic acid and 80 mol% or more of the glycol component is ethylene glycol. is there. Further, it may be a copolymer PET or a mixture of PET and another polyester.

<Polyamide resin>
As the polyamide resin used for the resin layer (β), those described above as the polyamide resin used for the resin layer (α) can be used. The polyamide resin in the resin layer (α) and the polyamide resin in the resin layer (β) may be the same or different.

<Polycarbonate resin>
Examples of the polycarbonate resin used for the resin layer (β) include various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method. Examples of the dihydroxy compound include hydroquinone, resorcinol, 4,4'-dihydroxy-diphenyl-methane, 4,4'-dihydroxy-diphenyl-ethane, 4,4'-dihydroxy-diphenyl-n-butane, 4,4'- Dihydroxy-diphenyl-heptane, 4,4'-dihydroxy-diphenyl-methane, 4,4'-dihydroxy-diphenyl-2,2-propane (bisphenol A), 4,4'-dihydroxy-3,3'-dimethyl- Diphenyl-2,2-propane, 4,4'-dihydroxy-3,3'-diphenyl-2,2-propane, 4,4'-dihydroxy-dichloro-diphenyl-2,2-propane, 4,4'- Dihydroxy-diphenyl-1,1-cyclopentane, 4,4′-dihydroxy-diphenyl-1,1-cycl Hexane, 4,4'-dihydroxy-diphenyl-methyl-phenyl-methane, 4,4'-dihydroxy-diphenyl-ethyl-phenyl-methane, 4,4'-dihydroxy-diphenyl-2,2,2-trichloro-1 , 1-ethane, 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy- 2,5-diethoxydiphenyl ether or the like is used. Among these, polycarbonate using 4,4′-dihydroxy-diphenyl-2,2-propane (bisphenol A) is preferable because of its excellent mechanical performance and transparency.

<Polyvinyl chloride resin>
Examples of the polyvinyl chloride resin forming the resin layer (β) include a vinyl chloride homopolymer or copolymer. The monomer copolymerizable with vinyl chloride is not particularly limited, and examples thereof include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or an ester thereof, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, and vinylidene chloride. Alternatively, a partially crosslinked resin may be used. Moreover, the mixture of these resin may be sufficient.
Of these, vinyl chloride homopolymers are preferred.

  The average degree of polymerization of polyvinyl chloride in the polyvinyl chloride resin is not particularly limited, but is usually 500 to 6000, preferably 800 to 30000. Further, the reduced viscosity (K value) of the polyvinyl chloride resin is not limited, but is usually 50 to 110, preferably 60 to 90 as a value based on JIS K7367-2.

[Other layers]
The laminated body of the present invention is a layer other than these layers, depending on the intended use, in addition to the resin layer (α), the resin layer (β), and an adhesive layer comprising the adhesive resin composition of the present invention. You may have.
The other layer that the laminate of the present invention may have is a layer that functions as a sealant layer for securing a sealing property as an innermost layer when cup-molded as a food or beverage container. Can be mentioned.

  Such a sealant layer is usually obtained by polymerizing or copolymerizing a polyolefin resin, preferably ethylene, propylene and 1-butene, which are α-olefins having 2 to 4 carbon atoms, alone or based on these. Crystalline polymers or copolymers, specifically, polyethylene resins, polypropylene resins, poly 1-butene resins, and the like are used. In addition, these are not limited to homopolymers, and other α-olefins having 2 to 20 carbon atoms or vinyl such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, and styrene, as long as the olefin is a main component. A copolymer with a compound is also included. Further, it may be a graft copolymer graft-modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, acrylic acid or a derivative thereof. Further, these polyolefin resins may be a mixture of two or more.

Specific examples of the polyethylene resin include, for example, high pressure method low density polyethylene (LDPE), ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene polymer, ethylene 1-hexene copolymer, high density polyethylene (HDPE), ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, and the like. Among these, LDPE, ethylene / α-olefin random copolymer, ethylene / vinyl acetate copolymer and the like are preferable because they are excellent in transparency and low-temperature heat sealability, and particularly have a density of 0.910 to 0.960 g. / Cm ³ and a melting point in the range of 100 to 135 ° C. are preferable. The MFR (JIS K7210-1 (2014) 190 ° C., load 2.16 kg) of the polyethylene resin is not particularly limited, but is usually 0.01 to 30 g / 10 minutes, further 0.03 from the viewpoint of moldability. Those in the range of ~ 28 g / 10 min are preferred.

  Specific examples of the polypropylene resin include, for example, polypropylene (propylene homopolymer), propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer, and propylene / 1-butene random copolymer. And a propylene-based random copolymer (propylene content is usually 90 mol% or more, preferably 95 mol% or more), or a propylene / ethylene block copolymer (ethylene content is usually 5 to 30 mol%). Among these, homopolymers and random copolymers are preferable because they are excellent in transparency, and random copolymers having a melting point of 130 to 150 ° C. are particularly preferable because they are excellent in heat sealability. In addition, although MFR (JIS K7210-1 (2014) 230 degreeC, load 2.16kg) of propylene-type resin is not specifically limited, From the point of a moldability, it is 0.5-30g / 10min normally, Furthermore, 0.5 Those in the range of ~ 28 g / 10 min are preferred.

  Specific examples of the poly-1-butene resin include, for example, 1-butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, 1-butene / 4-methyl-1-pentene. A copolymer is mentioned.

[Manufacturing method of laminate]
As a method for producing the laminate of the present invention using the adhesive resin composition of the present invention, known methods such as coextrusion molding, press molding, extrusion lamination molding and the like can be applied. Among these molding methods, the coextrusion molding method is preferably used in terms of interlayer adhesion. Coextrusion molding methods include a T-die method using a flat die and an inflation method using a circular die. The flat die may be either a single manifold type using a feed block or a multi-manifold type. Also, any known die can be used for the die used for the inflation method.

  As a method for producing a three-layer laminate comprising the aforementioned resin layer (α), an adhesive layer comprising the adhesive resin composition of the present invention and a resin layer (β), the resin of the resin layer (α) and the present invention Each of the adhesive resin composition and the resin of the resin layer (β) is melted by separate extruders and then supplied to a die having a multilayer structure, and the adhesive resin composition of the present invention is coextruded as an intermediate layer. Or a sand laminating method in which the adhesive resin composition of the present invention is melt-extruded between a preformed sheet of the resin layer (α) and a sheet of the polystyrene resin layer (β). .

  The above three-layer laminate is also applicable to a laminate having other layers such as the above-mentioned sealant layer, for example, a five-layer laminate of sealant layer / adhesive layer / resin layer (α) / adhesive layer / resin layer (β). In addition, in the production of, it can be produced by adding an extruding step of a sealant layer and an adhesive layer.

  In this case, the adhesive resin composition of the present invention is preferably used for adhesion between the resin layer (α) and the resin layer (β). For the adhesion between the sealant layer and the resin layer (α), it is not always necessary to use the adhesive resin composition of the present invention, but the adhesive resin composition of the present invention is the polyolefin resin described above constituting the sealant layer. In addition, the adhesive resin composition of the present invention can be suitably used because it exhibits excellent adhesiveness.

[Thickness of each layer]
In the laminate of the present invention, the thickness of the resin layer (α) is preferably 15 μm or more, more preferably 25 μm or more, and more preferably 35 μm or more for obtaining sufficient gas barrier properties by the resin layer (α). More preferably. On the other hand, from the viewpoint of the appearance of the laminate, it is preferably 150 μm or less, more preferably 140 μm or less, and further preferably 130 μm or less.

  Further, the thickness of the resin layer (β) is preferably 30 μm or more, more preferably 130 μm or more, and further preferably 230 μm or more in order to obtain sufficient rigidity by the resin layer (β). . On the other hand, from the viewpoint of the transparency of the laminate, it is preferably 1,200 μm or less, more preferably 1,100 μm or less, and even more preferably 1,000 μm or less.

  The thickness of the other layers is not particularly limited, but the above-mentioned sealant layer is preferably 30 μm or more, more preferably 40 μm or more, and more preferably 50 μm or more for obtaining sufficient sealing properties. More preferably. On the other hand, the thickness is preferably 800 μm or less, more preferably 500 μm or less, and even more preferably 200 μm or less from the viewpoint of thinning of the laminate and cost.

  The thickness of the adhesive layer of the adhesive resin composition of the present invention is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 5 μm or more from the viewpoint of adhesive strength. On the other hand, from the viewpoint of the appearance of the laminate, it is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 60 μm or less.

  The total thickness of the laminate of the present invention is preferably 50 μm or more, more preferably 100 μm or more, from the viewpoint of ensuring strength as a final product. On the other hand, from the viewpoint of improving the appearance of the final product, it is preferably 2,000 μm or less, more preferably 1,800 μm or less, and even more preferably 1,600 μm or less.

[Molded body]
The molded body of the present invention can be obtained by thermoforming the laminate of the present invention.
Specifically, a multilayer stretched molded product can be obtained by subjecting the laminate of the present invention to stretching treatment in a uniaxial direction or a biaxial direction. In addition, it is preferable to perform this extending | stretching process so that it may become 1.5 times or more by area ratio in a uniaxial direction or a biaxial direction.

  As the stretching method, after cooling and solidifying the unstretched laminated film or laminated sheet obtained by the above-described laminate manufacturing method, reheating to a stretching temperature of 60 to 160 ° C. inline or outline, a tenter, a plug, and The method of extending | stretching using compressed air etc. is mentioned. In this way, a molded container such as a film, cup, bottle or the like formed by uniaxial or biaxial stretching as a multilayer stretched molded product can be obtained.

  As a generally used forming method, in the case of an inflation film, an inflation simultaneous biaxial stretching method, in the case of a T-die film, a tenter simultaneous biaxial stretching method, a sequential biaxial stretching method using a roll and a tenter, and the like can be mentioned. . In the case of a cup, compressed air molding using only compressed air or the like in a mold, or stretched pneumatic molding using a plug and compressed air (SPPF molding), etc. In the case of a bottle, the laminated pipe is stretched vertically and then in the mold. Test tube bottomed parison is formed by pipe drawing method or injection molding that stretches horizontally with compressed air, etc., and the bottomed parison is stretched longitudinally with a rod in a mold and then stretched laterally with compressed air, etc. Examples thereof include a bottomed parison stretching method.

  In addition, the stretched laminate obtained by stretching the laminate of the present invention can be improved in heat resistance by reheating after stretching, that is, heat setting, if necessary.

  In addition, as an example of a preferable aspect of the molded body of the present invention, as shown in a specific example in the following examples, in the laminate of the present invention, the resin layer (α) is provided on the inner layer side, and the resin layer A molding cup having the (β) side on the outer layer side may be mentioned.

[Beverage containers]
The use of the laminate of the present invention and a molded product obtained by thermoforming the laminate is not particularly limited, but a laminate having both gas barrier properties by the resin layer (α) and rigidity by the resin layer (β), Since the adhesive resin composition of the present invention can be provided with good interlayer adhesion under a wide range of temperature conditions, the laminate and molded product of the present invention are used for food and beverage containers, particularly beverages. It can be suitably used as a container for goods, and can obtain sufficient interlayer adhesion durability as a container for hot beverages stored in a heat retaining case, a container for heating a microwave oven, a hot water extraction container, a high temperature sterilization container, etc. it can. When used as a beverage container, a beverage container having the resin layer (α) on the inner layer side and the resin layer (β) side on the outer layer side is particularly preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiment of the present invention, and preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

〔material〕
The detail of the raw material of the adhesive resin composition used in the following examples and comparative examples is as follows.

[Component (a)]
a-1: Polyethylene polymerized from a metallocene catalyst (density: 0.909 g / cm ³ , MFR (190 ° C., load 2.16 kg (JIS K7210-1 (2014))): 1.0 g / 10 min)
A-1 (for comparative example): polyethylene polymerized from a metallocene catalyst (density: 0.877 g / cm ³ , MFR (190 ° C., load 2.16 kg (JIS K7210-1 (2014))): 1.0 g / 10 minutes)
A-2 (for comparative example): polyethylene polymerized from Ziegler-Natta catalyst (density: 0.951 g / cm ³ , MFR (190 ° C., load 2.16 kg (JIS K7210-1 (2014))): 1. 0g / 10min)

[Component (b)]
b-1: Alcon (registered trademark) P-140 manufactured by Arakawa Chemical Co., Ltd. (softening point (ring ball method (JIS K6823)): (140 ± 5) ° C.)
b-2: Alcon (registered trademark) P-115 manufactured by Arakawa Chemical Co., Ltd. (softening point (ring-ball method (JIS K6823)): (115 ± 5) ° C.)

[Component (c)]
c-1: Maleic anhydride-modified polyethylene (MFR (190 ° C., load 2.16 kg (JIS K7210-1 (2014))): 0.5 g / 10 min, acid modification amount: 0.8 wt%)
c-2: Maleic anhydride-modified polyethylene (MFR (190 ° C., load 2.16 kg (JIS K7210-1 (2014))): 2.0 g / 10 min, acid modification amount: 0.4 wt%)

[Component (d)]
d-1: Styrene / ethylene butylene / styrene block copolymer (styrene block content: 42% by weight, melt viscosity (230 ° C., 60 s ⁻¹ ): 1,700 Pa · s, MFR (230 ° C., load 2. 16 kg (ISO-1133)): 0.8 g / 10 min)

[Other ingredients]
Phenol-based antioxidant: SONGNOX (registered trademark) 1010 manufactured by Songwon Co., Ltd.
Phosphorous antioxidant: SONGNOX (registered trademark) 1680 manufactured by Songwon Co., Ltd.
Neutralizer: Hydrotalcite DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.

[Examples and Comparative Examples]
[Example 1]
<Manufacture of adhesive resin composition>
60 parts by weight of a-1, b-1 of 20 parts by weight, c-1 of 10 parts by weight, d-1 of 10 parts by weight, phenolic antioxidant 0.1 part by weight, phosphorus antioxidant 0. 05 parts by weight and 0.05 parts by weight of a neutralizing agent were blended in advance by dry blending, using a twin screw extruder PCM45 (D = 45 mmφ, L / D = 34, manufactured by IKG Co., Ltd.), at a temperature of 200 ° C. Then, the mixture was melt-kneaded at a screw rotation speed of 300 rpm and an extrusion rate of 20 kg / h, extruded into a string, and cut after cooling to obtain pellets of an adhesive resin composition.
About the obtained adhesive resin composition, Vicat softening point and MFR were measured with the following method, and the result was shown in Table-1.

(Vicat softening point)
According to JIS K7151, the adhesive resin composition pellets were used to produce a press sheet having a thickness of 2 mm under the condition of 200 ° C. using a Shinto F type hydraulic press manufactured by Shinto Metal Industry. This was punched out with a test piece-shaped dumbbell, and the Vicat softening point was measured by the following method with reference to JIS K7206 (1999) as two layers.
Using a heat softening tester manufactured by Toyo Seiki Seisakusho (specification: S6-FH) as a heating device, increasing the load from 10N, 30 ° C to 0.5 ° C / min in a silicone oil bath (YF-33 manufactured by Toshiba Silicone Oil Co., Ltd.) It was measured by heating at a temperature rate. This measurement was performed three times and the average value was obtained.

(MFR)
According to JIS 7210-1 (2014), the measurement was performed at 190 ° C. and a load of 2.16 kg.

<Multilayer sheet>
Using the pellets of the adhesive resin composition obtained above as an adhesive layer, a multilayer sheet (laminate) was obtained with a co-extruded multilayer sheet molding machine manufactured by Pla Giken Co., Ltd.
At this time, the layer structure is polyethylene UF240 (manufactured by Nippon Polyethylene Co., Ltd., ethylene-butene copolymer, MFR (190 ° C., load 2.16 kg)): 2.0 g / from the side in contact with the cooling roll surface toward the outside. 10 minutes) / adhesive resin composition / EVAL (registered trademark) J171B (manufactured by Kuraray Co., Ltd., saponified ethylene-vinyl acetate copolymer, ethylene content: 32 mol%) / adhesive resin composition / HT478 (PS Japan) Polystyrene Co., Ltd., MFR (200 ° C., load 5 kg): 3.0 g / 10 min) (PE layer / adhesive layer / EVOH layer / adhesive layer / PS layer) was used. The thickness of each layer was 110 μm / 25 μm / 80 μm / 25 μm / 960 μm, the molding temperature was set to 220 ° C., and the molding speed was set to 1.0 m / min to obtain a multilayer sheet.

<Molded cup>
Using the multilayer sheet obtained by the coextrusion multilayer sheet molding machine, using a cup molding machine “RDM-50K” manufactured by ILLIG, molding temperature 260 ° C., molding speed 14 pieces / min, L / D = 0.6 To obtain a molded cup. At this time, the PE layer was placed inside the cup.

<Evaluation of room temperature adhesion>
A strip-shaped test piece having a width of 10 mm was cut out from the multilayer sheet and the molding cup obtained above. Next, a T-peel peel test was performed on the test piece in a precision universal testing machine AG2000 manufactured by Shimadzu Corporation under a 23 ° C. atmosphere at a speed of 50 mm / min (multilayer sheet) and a speed of 100 mm / min (molded cup). The adhesive strength was measured. The adhesive strength is preferably 10.0 N / cm or more for the multilayer sheet, and preferably 2.2 N / cm or more for the molded cup, and each was evaluated according to the following criteria. The results are shown in Table-1.
(Multilayer sheet)
○: Adhesive strength is 10.0 N / cm or more Δ: Adhesive strength is 7.0 N / cm or more and less than 10.0 N / cm x: Adhesive strength is less than 7.0 N / cm (molded cup)
○: Adhesive strength is 2.2 N / cm or more Δ: Adhesive strength is 1.7 N / cm or more and less than 2.2 N / cm x: Adhesive strength is less than 1.7 N / cm

<Evaluation of high temperature adhesiveness>
A strip-shaped test piece having a width of 10 mm was cut out from the multilayer sheet and the molding cup obtained above. Next, after leaving the test piece in a precision universal testing machine AG2000 manufactured by Shimadzu Corporation under an atmosphere of 95 ° C. for 3 minutes, T- at a speed of 50 mm / minute (multilayer sheet) and a speed of 100 mm / minute (molded cup). A peel peel test was performed to measure the adhesive strength. The adhesive strength is preferably 1.5 N / cm or more for both the multilayer sheet and the molded cup, and evaluated based on the following criteria. The results are shown in Table-1.
(Multilayer sheet and molded cup)
○: Adhesive strength is 1.5 N / cm or more Δ: Adhesive strength is 1.0 N / cm or more and less than 1.5 N / cm x: Adhesive strength is less than 1.0 N / cm

<Appearance evaluation>
Each of the multilayer sheet and molding cup obtained above was visually observed and evaluated according to the following criteria.
(Multilayer sheet and molded cup)
○: Appearance is good.
X: Unevenness, undulation, tearing, or lump is confirmed on the surface.

[Example 2 and Comparative Examples 1 to 4]
Except having changed the raw material and its compounding amount as shown in Table 1, pellets of the adhesive resin composition were obtained in the same manner as in Example 1, and the Vicat softening point and MFR were measured, respectively.
Using the adhesive resin composition pellets, multilayer sheets and molded cups were obtained in the same manner as in Example 1. And about these, evaluation similar to Example 1 was performed.
These results are shown in Table 1.

〔Evaluation results〕
As can be seen from Table 1, in Examples 1 and 2, laminates having good room temperature adhesiveness, high temperature adhesiveness, and appearance were obtained for both the multilayer sheet and the molding cup.

  On the other hand, Comparative Example 1 is an example in which the same layer structure as in Examples 1 and 2 and the adhesive layer was used and the component (d) was not used in the resin composition of the adhesive layer. In Comparative Example 1, the room temperature adhesiveness was poor.

  Comparative Example 2 has the same layer structure as that of Examples 1 and 2 except for the adhesive layer. In the resin composition of the adhesive layer, a metallocene catalyst was used instead of the component (a) from the resin composition used in Example 1. This is an example of using low-density polyethylene obtained by use. In Comparative Example 2, the high-temperature adhesiveness of the multilayer sheet and the molding cup were poor in high-temperature adhesiveness, and the appearance of the molding cup was also poor.

  Comparative Example 3 has the same layer structure as Examples 1 and 2 except for the adhesive layer. In the resin composition of the adhesive layer, a metallocene catalyst was used instead of the component (a) from the resin composition used in Example 1. This is an example in which a low-density polyethylene obtained by use and a high-density polyethylene obtained by using a Ziegler-Natta catalyst are used in combination. In Comparative Example 3, the multilayer sheet and the molded cup were slightly inferior in normal temperature adhesion and poor in high temperature adhesion.

  Comparative Example 4 has the same layer structure as Examples 1 and 2 except the adhesive layer, and the amount of component (a) is reduced from the resin composition used in Example 1 in the resin composition of the adhesive layer. This is an example in which the weight loss is replaced with low-density polyethylene obtained using a metallocene catalyst. In Comparative Example 4, the room temperature adhesiveness, high temperature adhesiveness and appearance of the multilayer sheet, and the molding cup high temperature adhesiveness and appearance were poor, and the molding cup had poor room temperature adhesiveness.

Claims (10)

From resin layer (α) selected from saponified ethylene-vinyl acetate copolymer and polyamide resin, adhesive layer, polystyrene resin, polyester resin, polyamide resin, polycarbonate resin, and polyvinyl chloride resin A laminate including a selected resin layer (β), wherein the adhesive layer includes the following component (a), component (b), component (c), and component (d), and components (a) to ( Component (a) is 45 to 85% by weight, Component (b) is 5 to 30% by weight, Component (c) is 5 to 30% by weight, and Component (d) is 5 to 20% by weight with respect to the total amount of d). A laminate comprising an adhesive resin composition containing 1%.
Component (a): Polyethylene resin component polymerized from a metallocene catalyst and having a density of 0.890 to 0.920 g / cm ³ (b): Alicyclic saturated hydrocarbon resin component (c): Acid-modified polyethylene resin component (d): hydrogenated block copolymer having an aromatic vinyl block and a conjugated diene block   The laminated body of Claim 1 whose content of the aromatic vinyl block of a component (d) is 20 to 65 weight%. Component (d) is a temperature 230 ° C., a melt viscosity at a shear rate of ^{60s -1} is 100~2,000Pa · s, laminate according to claim 1 or 2.   The laminated body of Claims 1 thru | or 3 whose softening point of a component (b) is 100-180 degreeC.   The laminate according to any one of claims 1 to 4, wherein the component (a) has a melt flow rate (MFR) at 190 ° C and a load of 2.16 kg of 0.1 to 10.0 g / 10 min. .   The adhesive resin composition has a Vicat softening point (JIS K7206 (1999)) of 70 to 100 ° C, a melt flow rate (MFR) at 190 ° C and a load of 2.16 kg of 0.1 to 10.0 g / 10. The laminate according to any one of claims 1 to 5, which is a minute.   The molded object formed by thermoforming the laminated body of any one of Claims 1 thru | or 6.   A molding cup formed by thermoforming the laminate according to any one of claims 1 to 6, having the resin layer (α) on the inner layer side and the resin layer (β) on the outer layer side.   A beverage container comprising the laminate according to any one of claims 1 to 6.   The container for beverages according to claim 9, which has the resin layer (α) on the inner layer side and has the resin layer (β) on the outer layer side.