JP2017210608A - Adhesive and laminate containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive and having excellent adhesion to a thermoplastic resin and an ethylene-vinyl alcohol copolymer.SOLUTION: Provided is an adhesive containing a thermoplastic resin (A), a copolymer (B) of ethylene and a vinyl ester and/or acrylic acid ester in which the content of vinyl ester and/or acrylic acid ester is greater by 5 mol% or more than that of (A), and a hydrolysate of a resin composition containing a product of (A) graft-modified with (B).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin (A), a copolymer of ethylene and vinyl ester and / or acrylic ester (B) having a vinyl ester and / or acrylic ester content of 5 mol% or more higher than (A), And (A) relates to an adhesive containing a hydrolyzate of a resin composition containing the modified product grafted by (B). The present invention also relates to a laminate comprising at least one layer composed of these adhesives.

  Packaging materials made of thermoplastic resins such as food, beverages, and pharmaceuticals are ethylene / vinyl alcohol copolymers (hereinafter referred to as “excellent gas barrier properties”, “scent retention”, “solvent resistance”, etc.) May be abbreviated as EVOH). However, since EVOH is hydrophilic and gas barrier properties and the like are lowered by moisture absorption, it is generally known that it is used for an intermediate layer of a laminate with polyolefin having excellent water resistance such as polyethylene and polypropylene. ing.

  Since EVOH has many hydroxyl groups in the molecule, it has a very low affinity with a thermoplastic resin having no polar group such as polyethylene and polypropylene, and the two do not generally adhere. For this reason, graft-modified ethylene-based resin compositions grafted with unsaturated carboxylic acids or derivatives thereof (for example, Patent Documents 1 and 2) and ethylene / vinyl acetate copolymer hydrolysates (for example, EVOH which is difficult to adhere to polyolefin) Patent Document 3) is already known to be used as an adhesive.

  The former graft-modified ethylene resin composition grafted with the former unsaturated carboxylic acid or its derivative has excellent adhesiveness, but because of its high reactivity with EVOH, when it is repeatedly kneaded, As the viscosity of the resin stays in the resin increases, the resin is colored and gelled. As a result, many fish eyes and gel-like substances are mixed in the product, resulting in a problem that the commercial value is lowered.

  On the other hand, the latter ethylene / vinyl acetate copolymer hydrolyzate does not cause coloring or gelation due to repeated kneading, and adhesion to EVOH is achieved by adding an adhesive resin to the ethylene / vinyl acetate copolymer hydrolyzate. However, the effect is small, and when it receives a small impact or friction during transportation or use, it often peels off and a sufficient adhesive force cannot be obtained.

  From such a background, there has been a demand for an adhesive that has superior adhesiveness and can be reused repeatedly.

JP 61-270155 A Japanese Patent Laid-Open No. Sho 62-158043 Japanese Patent Laid-Open No. 7-108655

  The present invention has been made in view of the above situation, and an object thereof is to provide an adhesive excellent in adhesiveness with thermoplastic resins such as polyethylene and polypropylene and EVOH, and a laminate comprising the same. To do.

  The above-mentioned problem is a thermoplastic resin (A), a copolymer of ethylene and vinyl ester and / or acrylic acid ester (B) having a vinyl ester and / or acrylic acid ester content of 5 mol% or more higher than (A), And (A) is solved by providing an adhesive containing a hydrolyzate of a resin composition containing the modified product grafted by (B).

  The present invention is described in detail below.

  The thermoplastic resin (A) of the present invention is a homopolymer of an α-olefin having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene or a copolymer thereof, ethylene and a vinyl ester and / or an acrylate ester. A copolymer of ethylene and a vinyl ester and / or an acrylate ester having a vinyl ester content and / or an acrylate ester content of 5 mol% or less less than the copolymer (B), polystyrene, styrenic polymer, poly Examples include vinyl chloride, polyester, and polyamide.

  For example, high pressure method low density polyethylene, high density polyethylene, medium density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl- 1-pentene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ethylene polymer such as ethylene / methacrylic acid ester copolymer, polypropylene, propylene / ethylene copolymer, propylene / Examples include 1-butene copolymer, poly 1-butene, poly 1-hexene, poly 4-methyl-1-pentene, and the thermoplastic resin (A) is used alone or in combination of two or more. Also good. Among these, from the viewpoint of adhesiveness with the thermoplastic resin layer and cost, high pressure method low density polyethylene, high density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, and polypropylene are preferable. The composition is most preferable because it is excellent in moldability.

  The method for producing the high-pressure low-density polyethylene can be exemplified by high-pressure radical polymerization, and such a resin can be conveniently selected from commercially available products, for example, commercially available under the trade name of Petrocene from Tosoh Corporation. ing. Production methods of high density polyethylene, ethylene / 1-butene copolymer and ethylene / 1-hexene copolymer are not particularly limited, but high and medium using Ziegler-Natta catalyst, Phillips catalyst, metallocene catalyst. -A low-pressure ion polymerization method etc. can be illustrated and such resin can be conveniently selected from a commercial item. For example, they are commercially available from Tosoh Corporation under the trade names Nipolon Hard, Nipolon-L and Nipolon-Z.

  The method for producing polypropylene is not particularly limited. For example, a catalyst typically formed from a solid titanium catalyst component and an organometallic compound catalyst component, or a catalyst formed from both components and an electron donor, Alternatively, it can be obtained by polymerizing propylene in the presence of a single site catalyst represented by a metallocene catalyst, or by copolymerizing propylene and one or more other α-olefins. Such a resin can be conveniently selected from commercially available products. For example, they are commercially available from Nippon Polypro Co., Ltd. under the names Novatec and Wintech.

  The copolymer (B) of ethylene and vinyl ester and / or acrylic ester of the present invention has a vinyl ester and / or acrylic ester content of 5 mol% or more than (A).

  Examples of the copolymer (B) of ethylene, vinyl ester, and acrylic acid ester include ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, and ethylene / methacrylic acid ester copolymer. Among these, an ethylene / vinyl acetate copolymer is preferable from the viewpoint of cost. Moreover, it is preferable that a vinyl ester and / or acrylic ester content are 10-35 mol% from an adhesive viewpoint with EVOH.

  The method for producing the ethylene / vinyl acetate copolymer is not particularly limited as long as the ethylene / vinyl acetate copolymer can be produced, but examples of the known high-pressure radical polymerization method and ionic polymerization method may be given. it can. As an ethylene / vinyl acetate copolymer produced by a high-pressure radical polymerization method, it is commercially available from Tosoh Corporation under the trade name of Ultrasen.

A suitable blending ratio of the composition is 5 to 95 parts by weight of the thermoplastic resin (A) and 5 to 95 parts by weight of ethylene and vinyl ester and / or acrylate ester (B) from the viewpoint of improving adhesion to both. Parts (total of (1) and (2) is 100 parts by weight), more preferably 15 to 85 parts by weight of the thermoplastic resin (A) and ethylene and vinyl ester and / or acrylic ester (B ) Is 15 to 85 parts by weight (total of (A) and (B) is 100 parts by weight), most preferably 20 to 80 parts by weight of the thermoplastic resin (A) and ethylene and vinyl ester and / or acrylate ( B) contains 20 to 80 parts by weight (the sum of (A) and (B) is 100 parts by weight).

  The graft modification method of the thermoplastic resin (A), ethylene, vinyl ester and / or acrylate ester (B) is not particularly limited as long as it can be graft-modified, and is appropriately selected in consideration of reactivity and the like. (A) a method of graft copolymerizing ethylene and vinyl acetate, (B) a method of grafting ethylene alone, ethylene and α-olefin, (A) and (B) are prepolymerized, and these are cross-linking agents Although the method of graft-modifying by (C) is mentioned, it is preferable to add a crosslinking agent (C) to the said (A) and (B) component from a viewpoint of productivity. When the thermoplastic resin (A) is polyethylene or polypropylene, it is most preferable to use an organic oxide as the crosslinking agent (C).

  The organic peroxide of the crosslinking agent (C) is not particularly limited as long as it is an organic peroxide. For example, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) ) Benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,3-di- (t-butylperoxy) -diisopropylbenzene, n-butyl-4,4-bis ( t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl Peroxybenzoate, t- butyl peroxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, may be such as t-butyl cumyl peroxide is exemplified. These can be used alone or in admixture of two or more.

  Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,1-di (t-butylperoxy) cyclohexane are preferably used from the viewpoint of reactivity. Moreover, you may use crosslinking adjuvants, such as a triallyl isocyanurate and divinylbenzene, as needed with the said crosslinking agent (C).

  The blending amount of the crosslinking agent (C) with respect to 100 parts by weight of the thermoplastic resin (A) and the copolymer of ethylene and vinyl ester and / or acrylate ester (B) is in the range of 0.005 to 1 part by weight. It is preferable from the viewpoints of improving adhesion to EVOH and moldability.

  The resin composition in which at least a part of the thermoplastic resin (A) of the present invention is grafted with a copolymer (B) of ethylene and a vinyl ester and / or an acrylic ester is the above-mentioned (A), (B) When manufacturing a graft body using (C) component, the method of melt-kneading these is preferable from an economical viewpoint.

  The melt-kneading method is not particularly limited as long as it is a melt-kneader that can uniformly disperse each component, and can be produced by a commonly used resin mixing device. Examples thereof include melt kneading apparatuses such as a single screw extruder, a multi-screw extruder, a Banbury mixer, a pressure kneader, and a rotary roll. Among them, a twin screw extruder having a high kneading degree and capable of being continuously operated is preferable because the dispersion state can be made fine and uniform. The melting temperature is preferably about the melting point of the thermoplastic resin (A) to about 260 ° C.

  The specific example of the manufacturing process of the resin composition by which at least one part of the thermoplastic resin (A) of this invention was grafted by the copolymer (B) of ethylene, vinyl ester, and / or acrylic ester is as follows. is there.

  The dry blend of the components (A) to (C) is charged into a hopper of an extruder. You may add at least one part of a thermoplastic resin (A), the copolymer (B) of ethylene, vinyl ester, and / or an acrylic ester, and a crosslinking agent (C) from a side feeder etc. Further, two or more extruders may be used, and the melt kneading may be sequentially performed step by step. For mixing the components (A) to (C), a Henschel mixer, a V blender, a ribbon blender, a tumbler, or the like may be used.

  In addition to the above components, a resin composition in which at least a part of the thermoplastic resin (A) of the present invention is grafted with a copolymer (B) of ethylene and a vinyl ester and / or an acrylate ester is necessary. Add additives that are usually used for thermoplastic resins such as crosslinking aids, antioxidants, lubricants, neutralizers, antiblocking agents, surfactants, slip agents, and other thermoplastic resins such as polyolefins. It does not matter if you do it.

  Further, the resin composition in the present invention is preferably a resin composition in which a thermoplastic resin (A) or a resin containing a copolymer (B) of ethylene and a vinyl ester and / or an acrylic ester is dispersed. . At this time, it is preferable that the dispersed particle diameter of the resin containing the thermoplastic resin (A) or the copolymer (B) of ethylene and a vinyl ester and / or an acrylic ester is 0.01 to 50 μm.

  The method for hydrolyzing the resin composition of the adhesive in the present invention is not particularly limited, but from the viewpoint of productivity, it is preferable to directly hydrolyze the pellet or powder of the resin composition in an alkali. The adhesive of the present invention preferably has a saponification degree of 10 mol% or more of the vinyl ester and / or acrylate component. If it is 10 mol% or more, the adhesiveness to EVOH is sufficient.

In addition, the complex elastic modulus G * ((storage elastic modulus G ′ ² + loss elastic modulus G ″ ² ) ^1/2 ) obtained by dynamic viscoelasticity measurement of the hydrolyzate in the present invention is 500 Pa. The loss angle δ (arctan (G ″ / G ′)), which is the phase angle between strain and stress or deflection and load, is 80 degrees or less, from the viewpoint of improving adhesion to polyolefins such as polyethylene and polypropylene, and EVOH Is preferable.

  The adhesive of the present invention can be used in any form such as pellets or powder.

  Furthermore, you may use the adhesive agent of this invention as a laminated body which consists of a layer which consists of this adhesive agent, and at least 1 layer which consists of another raw material.

  The laminate of the present invention preferably has a layer comprising the adhesive, at least one polyolefin such as polyethylene or polypropylene, polyester such as polylactic acid or polybutylene terephthalate, polyamide such as nylon, and EVOH layer. Moreover, you may have a laminated structure which has these 2 or more sets of combinations, and the combination of various thermoplastic resin layers. In particular, those having polyethylene or polypropylene and EVOH are preferable from the viewpoint of cost and moldability.

  The laminate of the present invention can be molded using a normal molding apparatus. Examples of the molding process include extrusion molding, blow molding, sheet molding, injection molding, compression molding, calendar molding, and vacuum molding. Arbitrary methods such as, can be formed into a sheet shape, film shape, pipe shape, block shape or any other shape, and by adopting a laminated structure with other materials, the laminated body has a gas barrier property It is possible to impart properties of other materials such as mechanical properties, oil resistance, and weather resistance.

  The laminate of the present invention can be used for packaging materials and containers made of thermoplastic resins such as foods, beverages, and pharmaceuticals that require these properties.

  The adhesive of this invention is excellent in adhesiveness with thermoplastic resins, such as polyethylene and polypropylene, and EVOH, and can adhere a thermoplastic resin and EVOH.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[Saponification degree]
Each adhesive obtained from the examples was measured according to JIS K7192 (1999).
[Dispersed particle size]
Each adhesive obtained from the examples was press-molded using a 50-ton automatic press machine manufactured by Shinto Kogyo Co., Ltd. Subsequently, a cross-section of the press-formed product was prepared using a cryomicrotome (Ultra Microtome MT-XL + CR-X manufactured by RMC-Boeckeler), and Ar plasma etching (2 W, 10 min) was performed on the prepared surface. After the Os coat was applied to the etched surface, the dispersed particle size was evaluated by SEM observation (SEM VE-9800 manufactured by Keyence).
[Adhesive strength]
The adhesiveness with each adherend (LDPE or PP, and EVOH) was investigated using each adhesive obtained from the examples. The procedure for evaluating the adhesive strength is as follows. About 4 g of each pellet was press-molded using a 50-ton automatic press machine manufactured by Shindo Kogyo Co., Ltd. The size of the molded product was 150 mm × 150 mm × 0.1 mm. Subsequently, using a hot tack tester manufactured by Tester Sangyo Co., Ltd., the adhesive and the adherend are heat sealed by heating up and down at a sealing temperature of 200 ° C., a sealing pressure of 0.1 MPa, and a sealing time of 1 second, and a tensile tester. Using TENENTRON RTE-1210 (ORIENTEC), the adhesive strength (N / 15 mm width) at 180 ° peeling was measured at a sample width of 15 mm and a tensile speed of 300 mm / min. The LDPE, PP, PS, and EVOH used for evaluation were as shown below.
(1) LDPE: Low-density polyethylene having a melt mass flow rate of 7 g / 10 min and a density of 922 kg / m ³ (trade name: Petrocene 204, manufactured by Tosoh Corporation)
(2) PP: polypropylene having a melt mass flow rate of 6.5 g / 10 min and a density of 900 kg / m ³ (product name: Novatec FW4BT, manufactured by Nippon Polypro Co., Ltd.)
(3) PS: polystyrene having a melt mass flow rate of 2.4 g / 10 min (manufactured by DIC Corporation, trade name GH-8300-1)
(4) EVOH: Melt mass flow rate of 5.7 g / 10 min, ethylene / vinyl alcohol copolymer having an ethylene content of 44 mol% (Kuraray Co., Ltd., trade name: EVAL E105B)
Example 1
As the thermoplastic resin composition (A), 70 parts by weight of low density polyethylene (trade name Petrocene 350, manufactured by Tosoh Corporation) having a melt mass flow rate of 16 g / 10 min and a density of 920 kg / m ³ , ethylene and vinyl ester, and / or Alternatively, as a copolymer (B) with an acrylate ester, an ethylene / vinyl acetate copolymer having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight (manufactured by Tosoh Corporation, product) 30 parts by weight of Ultrasen 760, abbreviated as EVA hereinafter, and 0.1 parts by weight of organic peroxide (trade name Perhexa 25B, manufactured by NOF Corporation) as a crosslinking agent (C) Blending was carried out at a molten resin temperature of 190 ° C., and the mixture was melt-kneaded with a twin-screw extruder to obtain a pellet-shaped graft body. Subsequently, the graft body was hydrolyzed in a 1 part by weight sodium hydroxide methanol solution at 60 ° C. to obtain the present adhesive (degree of saponification: 75 mol%, dispersed particle size: 0.1 to 2 μm). It was. Using the obtained adhesive, the adhesion to LDPE and EVOH was evaluated, and as shown in Table 1.

Example 2
As the thermoplastic resin composition (A), 50 parts by weight of low density polyethylene (trade name Petrocene 350, manufactured by Tosoh Corporation) having a melt mass flow rate of 16 g / 10 min and a density of 920 kg / m ³ , ethylene and vinyl ester and / or Alternatively, as a copolymer (B) with an acrylate ester, an ethylene / vinyl acetate copolymer having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight (manufactured by Tosoh Corporation, product) The adhesive was manufactured in the same manner as in Example 1 except that 50 parts by weight of Ultrasen 760) was used to obtain the present adhesive (degree of saponification: 75 mol%, dispersed particle size: not observable). When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 3
As the thermoplastic resin composition (A), 30 parts by weight of low density polyethylene (trade name Petrocene 350, manufactured by Tosoh Corporation) having a melt mass flow rate of 16 g / 10 min and a density of 920 kg / m ³ , ethylene and vinyl ester, and / or Alternatively, as a copolymer (B) with an acrylate ester, an ethylene / vinyl acetate copolymer having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight (manufactured by Tosoh Corporation, product) This adhesive was manufactured in the same manner as in Example 1 except that the name Ultrasen 760) was changed to 70 parts by weight to obtain the present adhesive (degree of saponification: 75 mol%, dispersed particle size: 0.1 to 2 μm). When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 4
70 weights of thermoplastic resin composition (A), low-density polyethylene (made by Tosoh Corporation, trade name Nipolon-LM65, hereinafter abbreviated as LLDPE) having a melt mass flow rate of 20 g / 10 min and a density of 920 kg / m ³ Ethylene / vinyl acetate copolymer having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight as a copolymer (B) of ethylene and vinyl ester and / or acrylic ester This adhesive was manufactured in the same manner as in Example 1 except that 30 parts by weight (trade name Ultrasen 760 manufactured by Tosoh Corporation) was used, and this adhesive (degree of saponification: 75 mol%, dispersed particle size: 0.1 to 0.1) 2 μm) was obtained. When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 5
As thermoplastic resin composition (A), 70 parts by weight of polypropylene having a melt mass flow rate of 6.5 g / 10 min and a density of 900 kg / m ³ (manufactured by Nippon Polypro Co., Ltd., trade name Novatec FW4BT, hereinafter abbreviated as PP) As a copolymer (B) of ethylene and vinyl ester and / or acrylic ester, an ethylene / vinyl acetate copolymer having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight ( This adhesive was manufactured in the same manner as in Example 1 except that Tosoh Co., Ltd., trade name Ultrasen 760 was changed to 30 parts by weight, and this adhesive (degree of saponification: 75 mol%, dispersed particle size: 0.1 to 2 μm) ) When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 6
As the thermoplastic resin composition (A), an ethylene / vinyl acetate copolymer having a melt mass flow rate of 14/10 minutes, a density of 935 kg / m ³ and a vinyl acetate content of 15% by weight (trade name Ultrasen 625, manufactured by Tosoh Corporation) ), 70 parts by weight of ethylene / vinyl ester and / or acrylate ester (B), ethylene / acetic acid having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight 30 parts by weight of vinyl copolymer (manufactured by Tosoh Corporation, trade name Ultrasen 760) and 0.001 of organic peroxide (trade name: Perhexa C, manufactured by NOF Corporation) as a crosslinking agent (C) The adhesive was produced in the same manner as in Example 1 except that dry blending was performed in the proportion of parts by weight to obtain the present adhesive (degree of saponification: 20 mol%, dispersed particle size: 0.1 to 2 μm). . When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 7
The adhesive was produced in the same manner as in Example 6 except that 0.1 part by weight of the cross-linking agent (C-2) was added to obtain the present adhesive (degree of saponification: 20 mol%, dispersed particle size: 0.1 to 2 μm). It was. When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 8
As the thermoplastic resin composition (A), an ethylene / vinyl acetate copolymer having a melt mass flow rate of 14 g / 10 min, a density of 935 kg / m ³ , and a vinyl acetate content of 15% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 625) ), 70 parts by weight of a copolymer of ethylene and vinyl ester and / or acrylate ester (B), an ethylene / vinyl acetate copolymer having a vinyl acetate content of 70% by weight (manufactured by Nippon Synthetic Chemical Co., Ltd. The present adhesive (degree of saponification: 25 mol) was prepared in the same manner as in Example 1 except that 30 parts by weight of Soabrene DH) and 0.1 parts by weight of the crosslinking agent (C-2) were dry blended. %, Dispersed particle size: 0.1 to 2 μm). When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 9
As the thermoplastic resin composition (A), an ethylene / vinyl acetate copolymer having a melt mass flow rate of 5.7 / 10 minutes, a density of 952 kg / m ³ , and a vinyl acetate content of 28% by weight (trade name Ultra manufactured by Tosoh Corporation) 7075 parts by weight of Sen 751), melt mass flow rate of 70 g / 10 min, density of 968 kg / m ³ , vinyl acetate content of 42% by weight of ethylene / vinyl acetate copolymer (trade name Ultrasen 760, manufactured by Tosoh Corporation) The adhesive was produced in the same manner as in Example 1 except that the amount was 30 parts by weight to obtain the present adhesive (degree of saponification: 40 mol%, dispersed particle size: 0.1 to 2 μm). When the obtained adhesive was evaluated, it was as shown in Table 1.

Example 10
30 as a thermoplastic resin composition (A), a hydrogenated styrene-based thermoplastic elastomer having a melt mass flow rate of 65 g / 10 min (200 ° C., 5.0 kg) (trade name KRATON: G1726, manufactured by Kraton Polymer Japan Co., Ltd.) 70 parts by weight of ethylene / vinyl acetate copolymer (trade name Ultrasen 760, manufactured by Tosoh Corporation) having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ , and a vinyl acetate content of 42% by weight Except for the above, it was produced in the same manner as in Example 1 to obtain the present adhesive (degree of saponification: 40 mol%, dispersed particle size: 0.1 to 2 μm). When the obtained adhesive was evaluated, it was as shown in Table 1.

比較例１
熱可塑性樹脂組成物（Ａ）として、メルトマスフローレート１６ｇ／１０分、密度９２０ｋｇ／ｍ^３の低密度ポリエチレン（東ソー（株）製、商品名ペトロセン３５０）に架橋剤（Ｃ−１）を０．１重量部の割合でドライブレンドした以外は実施例１と同様の方法で製造し本接着剤（ケン化度：７０ｍｏｌ％）を得た。得られた接着剤を用いて評価したところ、ＥＶＯＨに対する接着性が低かった。結果を表２に示す。

Comparative Example 1
As the thermoplastic resin composition (A), a cross-linking agent (C-1) was added to low-density polyethylene (trade name Petrocene 350, manufactured by Tosoh Corporation) having a melt mass flow rate of 16 g / 10 min and a density of 920 kg / m ³ . This adhesive (saponification degree: 70 mol%) was obtained by the same method as in Example 1 except that dry blending was performed at a ratio of 1 part by weight. When evaluated using the obtained adhesive, adhesion to EVOH was low. The results are shown in Table 2.

Comparative Example 2
As a copolymer (B) of ethylene and a vinyl ester and / or an acrylic ester, an ethylene / vinyl acetate copolymer having a melt mass flow rate of 70 g / 10 min, a density of 968 kg / m ³ and a vinyl acetate content of 42% by weight (Tosoh Corporation) This adhesive (degree of saponification) was manufactured in the same manner as in Example 1 except that the cross-linking agent (C-2) was dry blended at a ratio of 0.1 part by weight to the product name Ultrasen 760, manufactured by Co., Ltd. : 70 mol%). When evaluated using the obtained adhesive, adhesion to EVOH was low. The results are shown in Table 2.

Comparative Example 3
Except not using a crosslinking agent, it manufactured by the same method as Example 1, and obtained this adhesive agent (saponification degree: 75 mol%). When evaluated using the obtained adhesive, adhesion to EVOH was low. The results are shown in Table 2.

Comparative Example 4
The adhesive was produced in the same manner as in Example 1 except that the hydrolysis treatment was not performed to obtain the present adhesive (degree of saponification: 0 mol%). When evaluated using the obtained adhesive, adhesion to EVOH was low. The results are shown in Table 2.

Claims (14)

  Thermoplastic resin (A), copolymer of ethylene and vinyl ester and / or acrylic ester (B) having a vinyl ester and / or acrylic ester content of 5 mol% or more higher than (A), and (A) An adhesive comprising a hydrolyzate of a resin composition containing the modified product grafted by (B).   2. The adhesive according to claim 1, wherein the dispersed particle diameter of the resin containing (A) or (B) is 0.01 to 50 [mu] m.   The adhesive according to claim 1 or 2, wherein the thermoplastic resin (A) contains at least one homopolymer of C2-C12 α-olefin or a copolymer thereof.   Ethylene, vinyl ester and / or acrylic in which thermoplastic resin (A) has a vinyl ester content and / or acrylic ester content of 5 mol% or less less than copolymer (B) of ethylene and vinyl ester and / or acrylic ester The adhesive according to any one of claims 1 to 3, comprising at least one copolymer with an acid ester.   The vinyl ester content and / or the acrylic ester content of the copolymer (B) of ethylene and vinyl ester and / or acrylic ester is 5 to 35 mol%. The adhesive described.   The adhesive according to any one of claims 1 to 5, further comprising a crosslinking agent (C).   The adhesive according to claim 1, wherein the content of vinyl alcohol is 0.5 to 40 mol%, and the content of vinyl ester and / or acrylate is 30 mol% or less.   The laminated body containing the layer which consists of an adhesive agent in any one of Claims 1-7, and at least 1 layer which consists of another raw material.   The laminate according to claim 8, wherein the other material is an ethylene / vinyl alcohol copolymer.   The laminate according to claim 8 or 9, wherein the other material is a thermoplastic resin (A).   A laminate in which a layer containing an ethylene / vinyl alcohol copolymer, a layer made of the adhesive according to any one of claims 1 to 7, and a layer containing a thermoplastic resin (A) are sequentially laminated.   A blow molded article comprising the laminate according to any one of claims 8 to 11.   The sheet molded article which consists of a laminated body in any one of Claims 8-11.   The film molded product which consists of a laminated body in any one of Claims 8-11.