JP6291246B2 - Adhesive resin composition and laminate - Google Patents

Description

  The present invention relates to an adhesive resin composition, in particular, an adhesive resin composition excellent in adhesiveness with a hardly adhesive material such as a polyester resin, an adhesive resin composition between members such as a film, or The present invention relates to an adhesive resin composition used in a wide range of fields such as packaging materials for food, automobile parts, housing materials, electrical and electronic parts such as home appliances, and various industrial materials.

  Thermoplastic resins such as thermoplastic elastomers, olefin polymers, vinyl polymers, and engineering plastics are excellent in impact resistance properties, moldability, surface properties, etc. It is processed into a film and used in many fields such as automobiles, electrical / electronics, architecture, and miscellaneous goods. In order to make these molded products into products having a desired shape, or to improve performance and diversify functions, it is necessary to bond a plurality of molded products to form a composite. One such example is a barrier film. Polyester resins typified by polyethylene terephthalate resin are excellent in mechanical strength, rigidity, chemical resistance, etc., and therefore, film laminates having high barrier properties including polyester films are widely used as packaging materials for foods and the like. Yes.

  As the adhesive layer of these film laminates, usually, a urethane-based adhesive is often used. On the other hand, since no solvent is used in the bonding process, an olefin-based adhesive is used as a hot-melt adhesive. Adhesives are being developed. However, olefin-based adhesives have weak adhesion to resin films such as polyester films because of the low polarity of the olefin itself. Therefore, a resin or the like obtained by modifying an olefin with a polar group or the like has been proposed, but its adhesiveness is not yet sufficient, and improvement has been desired.

  Adhesives based on olefin resins include those composed of styrene elastomers, ethylene / α-olefin copolymers grafted with unsaturated carboxylic acids or their derivatives and vinyl acetate (Patent Document 1), modified Known are those composed of styrene thermoplastic elastomers, polyolefin resins, tackifiers (Patent Document 2), modified polyolefins, non-modified polyolefins (Patent Document 3), and the like.

Japanese Patent No. 2909169 JP2012-107115A Japanese Patent No. 2656818

  The problem to be solved by the present invention is to provide a polyolefin-based adhesive resin that exhibits excellent adhesion to a hardly-adhesive substrate and also has flexibility while maintaining processability.

  As a result of intensive studies in view of the above-described problems, the present inventors have found that an adhesive resin composition containing modified polyolefin, low-density polyethylene or linear low-density polyethylene, and a styrene-based thermoplastic elastomer as essential components makes it difficult to adhere. The present inventors have found that excellent adhesion performance is exhibited with respect to this film, and have completed the following invention.

That is, the present invention relates to a modified polyolefin (A) having a tensile modulus of 500 MPa to 1500 MPa, a low density polyethylene or linear low density polyethylene (B) having a density of 0.940 g / cm ³ or less, and a styrenic thermoplastic elastomer ( C), wherein the weight ratio of each component is 0.7 <C / (A + B) <1.1, and the tensile modulus of the adhesive resin composition is 100 MPa or less . The modified polyolefin (A) is produced by a modification step in which a polyolefin, an epoxy group-containing vinyl monomer and an aromatic vinyl monomer are melt-kneaded in the presence of a radical polymerization initiator. relative to the weight part, with an epoxy group-containing vinyl monomer is added 0.1 to 20 parts by weight adhesive resin composition you modified is there.

Upper Symbol epoxy group-containing vinyl monomer, a methacrylic acid ester or acrylic acid ester containing an epoxy group or it is preferred that the a derivatives of either.

  The styrenic thermoplastic elastomer (C) was selected from a styrene-isoprene block copolymer, a styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, a hydrogenated styrene-butadiene block copolymer, and a hydrogenated styrene-butadiene random copolymer. At least one kind is preferred.

  Further, the laminate of the present invention is a heat composed of at least one selected from the group consisting of polyolefin resins, styrene resins, polycarbonate resins, acrylic resins, polyamide resins, polyphenylene ether resins, and polyester resins. The layer of the plastic resin is bonded with the resin composition of the present invention.

  The resin composition of the present invention can ensure excellent adhesion to difficult-to-adhere substrates, and has suitable processability.

Details of the present invention will be described below.
(Adhesive resin composition)
The adhesive resin composition in the present invention includes a modified polyolefin (A) having a tensile modulus of 500 MPa to 1500 MPa, a low density polyethylene or a linear low density polyethylene (B) having a density of 0.940 g / cm ³ or less, and styrene. An adhesive resin composition (C) comprising a thermoplastic elastomer, wherein the adhesive resin composition has a tensile modulus of 100 MPa or less. The tensile elastic modulus of the adhesive resin composition is preferably 100 MPa or less, and when it exceeds 100 MPa, the adhesiveness is low.

(Weight ratio of each component)
The weight ratio of each component in the adhesive resin composition in the present invention is 0.7 <C / (A + B) <1.1, and more preferably 0.8 <C / (A + B) <1.1. preferable. When the weight ratio is smaller than 0.7, the elastic modulus of the resin composition is not sufficiently lowered and the adhesiveness is poor, and when the weight ratio exceeds 1.1, the modified polyolefin is relatively decreased. Therefore, the adhesiveness is poor, which is not preferable.
(Tensile modulus)
The tensile elastic modulus according to the present invention is an autograph using a test piece produced by punching with a 2 (1/3) dumbbell die in JIS K7113 from a sheet formed to a thickness of about 1 mm by a hot press. The tensile elastic modulus measured under the condition of a tensile speed of 50 mm / min (min) is meant.

((A) modified polyolefin)
The modified polyolefin resin according to the present invention is preferably a modified polyolefin resin obtained by melt-kneading the following (a), (b), (c) and (d) from the viewpoint of adhesiveness.
(A) 100 parts by weight of polyolefin resin,
(B) 0.01 parts by weight to 5 parts by weight of a radical polymerization initiator,
(C) 0.01-20 parts by weight of an epoxy group-containing vinyl monomer,
(D) 0.01-20 parts by weight of an aromatic vinyl monomer,
The modified polyolefin resin composition comprises (a) an unmodified polyolefin resin and (b) a radical polymerization initiator, in addition to (c) an epoxy group-containing vinyl monomer, and (d) an aromatic vinyl. A resin composition obtained by graft polymerization reaction in which a graft chain composed of a monomer is grafted is preferable from the viewpoint of increasing graft efficiency. Moreover, you may add various stabilizers and various additives to the modified polyolefin resin composition of this invention in the range which does not impair the effect of this invention as needed.

  The mode of the graft polymerization reaction used in the present invention is not particularly limited, but solution polymerization, impregnation polymerization, melt polymerization and the like can be used. In particular, melt polymerization is simple and preferable. The heating temperature at the time of melt kneading is preferably 100 to 250 ° C. from the viewpoint that the polyolefin resin is sufficiently melted and is not thermally decomposed. The time for melt kneading (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.

  Moreover, as said melt-kneading apparatus, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, etc. can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder is preferred. Moreover, in order to mix each material sufficiently uniformly, the said melt-kneading | mixing may be repeated in multiple times.

  (A) The tensile modulus of the modified polyolefin is preferably 500 MPa or more and 1500 MPa, and when it is lower than 500 MPa, the pellets are adhered to each other when granulating in the modification step, and metal soap or the like is added during granulation. This is not preferable because it requires a large amount of equipment and handling. Moreover, when it exceeds 1500 MPa, since the tensile elasticity modulus of an adhesive resin composition does not fall sufficiently, it is unpreferable.

((A) polyolefin)
Examples of the polyolefin (a) include polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, ethylene / α-olefin copolymer, ethylene / α-olefin / diene copolymer, ethylene / Polyolefin such as butene-1 copolymer, cyclic polyolefin such as copolymer of cyclopentadiene and ethylene and / or propylene, ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA) ), Polyolefins having a polar group introduced, such as an isobutylene / maleic anhydride copolymer. Among these, since the modification reaction is easy, it is preferable to use one or two or more selected from polyethylene, polypropylene, ethylene / α-olefin copolymer, and polymethylpentene, and polyethylene, polypropylene, ethylene / It is more preferable to use one or more selected from α-olefin copolymers, and it is particularly preferable to use one or more selected from polypropylene and ethylene / α-olefin copolymers. preferable.

((B) radical initiator)
Examples of the radical polymerization initiator generally include peroxides and azo compounds, but those having high hydrogen abstraction ability are preferred. Examples of such radical polymerization initiator include 1,1-bis (t-butyl). Peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis Peroxyketals such as (t-butylperoxy) butane; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylper Oxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl) Luperoxy) Dialkyl peroxides such as hexyne-3; Diacyl peroxides such as benzoyl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy -3,5,5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy Examples thereof include peroxyesters such as benzoate and di-t-butylperoxyisophthalate, and it is preferable to use one or more of them.

  The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the non-modified polyolefin resin (a), and 0.05 to 3 parts by weight. More preferably, it is within the range. If the amount is less than 0.01 part by weight, the graft polymerization does not proceed sufficiently, and if it exceeds 5 parts by weight, the melt viscosity and mechanical properties of the polyolefin resin are significantly lowered.

((C) epoxy group-containing vinyl monomer)
Examples of the epoxy group-containing vinyl monomer include glycidyl methacrylate (GMA), glycidyl acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, p -Glycidyl styrene carboxylate, allyl glycidyl ether, methacryl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, Examples thereof include epoxy olefins such as 4-hydroxybutyl glycidyl ether of acrylic acid (4HBAGE), vinylcyclohexene monoxide, and the like. Among these, glycidyl methacrylate, glycidyl acrylate, and 4-hydroxybutyl glycidyl acrylate are preferable in terms of low cost, and glycidyl methacrylate is particularly preferable. Said epoxy group containing vinyl monomer can be used individually or in mixture of 2 or more types. The addition amount of the epoxy group-containing vinyl monomer is 0.01 to 20 parts by weight with respect to 100 parts by weight of the non-modified polyolefin resin (a) from the viewpoint of sufficiently ensuring the adhesiveness. Preferably, it is 0.1-15 weight part, More preferably, it is 0.1-10 weight part. If the amount added exceeds 20 parts by weight in the above range, the processability of the modified polyolefin deteriorates, and if it is less than 0.01 parts by weight, sufficient adhesiveness is not exhibited.

((D) aromatic vinyl monomer)
Examples of the aromatic vinyl monomer (d) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, dimethylstyrene, and trimethylstyrene. chlorostyrene such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, Bromostyrene such as dibromostyrene and tribromostyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, fluorostyrene such as trifluorostyrene, o-nitrostyrene, m-nitrostyrene, p-nitrostyrene Nitrostyrene such as dinitrostyrene and trinitrostyrene, vinylphenol such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene and trihydroxystyrene, o-divinylbenzene, m-divinylbenzene, p- Examples include divinylbenzene such as divinylbenzene, o-diisopropenylbenzene, m-diisopropenylbenzene, and diisopropenylbenzene such as p-diisopropenylbenzene, and the aromatic vinyl monomer (d) is It can use individually or in mixture of 2 or more types. Of the above, methylstyrene such as styrene, α-methylstyrene, and p-methylstyrene, divinylbenzene monomer, or divinylbenzene isomer mixture is preferable because it is inexpensive, and styrene is particularly preferable.

  The amount of the aromatic vinyl monomer (d) added is 0.01% with respect to 100 parts by weight of the polyolefin (a) from the viewpoint of the moldability of the modified polyolefin and the reaction efficiency of the epoxy group-containing vinyl monomer. It is preferably ˜20 parts by weight, more preferably 0.1 to 15 parts by weight, and particularly preferably 0.1 to 10 parts by weight. If the amount added exceeds 20 parts by weight, the processability of the modified polyolefin deteriorates, and if it is less than 0.01 parts by weight, the reaction efficiency of the epoxy group-containing vinyl monomer deteriorates. .

((B) low density polyethylene or linear low density polyethylene)
The low-density polyethylene or linear low-density polyethylene is not particularly limited as long as the density is 0.940 g / cm ³ or less. When polyethylene having a density exceeding 0.940 g / cm ³ is used, the adhesiveness is low.

(Styrenic thermoplastic elastomer)
The styrenic thermoplastic elastomer is not particularly limited as long as it is a thermoplastic elastomer containing styrene, a homologue thereof or an analogue thereof. Specific examples of the styrenic thermoplastic elastomer include at least one block of styrene, a homologue thereof or an analogue thereof as an end block, and at least one elastomer block of a conjugated diene or a hydrogenated product thereof. Can be mentioned as a block copolymer. Preferred examples include styrene-butadiene diblock copolymer, styrene-butadiene triblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene triblock. Examples include copolymers, hydrogenated styrene-isoprene diblock copolymers, hydrogenated styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene random copolymers. Furthermore, in addition to styrene, the styrene block may contain a copolymer of styrene and an aromatic vinyl compound such as α-methylstyrene. Among these styrenic elastomers, from the viewpoint of heat resistance and weather resistance, it is preferable that some or all of unsaturated double bonds in the polymer block mainly composed of the conjugated diene are hydrogenated. It is particularly preferred to use styrene-isoprene triblock copolymer (SEPS), hydrogenated styrene-butadiene triblock copolymer (SEBS), hydrogenated styrene-butadiene random copolymer (HSBR). Said (styrene-type thermoplastic elastomer) can be used individually or in mixture of 2 or more types.

(Laminate)
The laminate according to the present invention is a thermoplastic resin layer comprising at least one selected from the group consisting of polyolefin resins, styrene resins, polycarbonate resins, acrylic resins, polyamide resins, and polyester resins. Is a laminate formed by bonding with the adhesive resin composition of the present invention. Although there is no restriction | limiting in particular in the lamination method, Extrusion lamination etc. are mentioned.

Specific examples are shown below, but the present invention is not limited to the following examples.
Example 1
(A) Random polypropylene (manufactured by Prime Polymer Co., Ltd .: S235WC) 100 parts by weight, (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, halved for 1 minute 175 ° C) 0.4 parts by weight were supplied to a twin screw extruder (46 mmφ, L / D = 60, manufactured by Kobe Steel, product name HYPERKTX46) set at a cylinder temperature of 200 ° C and a rotation speed of 150 rpm. After melt-kneading to obtain pellets by melt-kneading, 4 parts by weight of glycidyl methacrylate and 4 parts by weight of styrene were then added and melt-kneaded from the middle of the cylinder to obtain modified polyolefin (A1). 25 parts by weight of the modified polyolefin (A1) obtained above, 25 parts by weight of low density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), 50 hydrogenated styrene thermoplastic elastomer (manufactured by JSR Co., Ltd .: DYNARON1321P) 50 Weight parts were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (A2). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Example 2)
25 parts by weight of the modified polyolefin (A1) obtained above, 30 parts by weight of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd .: Tuftec H1221) 45 parts by weight were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (A3). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Example 3)
30 parts by weight of the modified polyolefin (A1) obtained above, 25 parts by weight of low density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd .: Tuftec H1221) 45 parts by weight were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (A4). The adhesive strength and tensile elastic modulus were measured by the following methods.

Example 4
(A) 100 parts by weight of random polypropylene (manufactured by Prime Polymer Co., Ltd .: B221WA), (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, halved for 1 minute 175 ° C) 0.4 parts by weight were supplied to a twin screw extruder (46 mmφ, L / D = 60, manufactured by Kobe Steel, product name HYPERKTX46) set at a cylinder temperature of 200 ° C and a rotation speed of 150 rpm. After melt-kneading to obtain a pellet obtained by melt-kneading, 4 parts by weight of glycidyl methacrylate and 4 parts by weight of styrene were added from the middle of the cylinder and melt-kneaded to obtain a modified polyolefin (A5). 25 parts by weight of the modified polyolefin (A5) obtained above, 25 parts by weight of low density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd .: Tuftec H1221) 50 parts by weight were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (A6). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Example 5)
(A) 100 parts by weight of block polypropylene (manufactured by Prime Polymer Co., Ltd .: E701G), (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, halved for 1 minute 175 ° C) 0.4 parts by weight were supplied to a twin screw extruder (46 mmφ, L / D = 60, manufactured by Kobe Steel, product name HYPERKTX46) set at a cylinder temperature of 200 ° C and a rotation speed of 150 rpm. After melt-kneading to obtain a pellet obtained by melt-kneading, 4 parts by weight of glycidyl methacrylate and 4 parts by weight of styrene were then added and melt-kneaded from the middle of the cylinder to obtain a modified polyolefin (A7). 25 parts by weight of the modified polyolefin (A7) obtained above, 25 parts by weight of low density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd .: Tuftec H1221) 50 parts by weight were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (A8). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Comparative Example 1)
Using the modified polyolefin (A1) obtained above as an adhesive resin, the adhesive strength and tensile elastic modulus were measured by the following methods.

(Comparative Example 2)
Resin kneading machine in which 50 parts by weight of the modified polyolefin (A1) obtained in Example 1 and 50 parts by weight of a hydrogenated styrene thermoplastic elastomer (manufactured by JSR Corporation: DYNARON1321P) were set at a temperature of 200 ° C. ) Kneaded with Toyo Seiki, product name Lab Plast Mill) to obtain an adhesive resin (B1). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Comparative Example 3)
Resin kneader (Co., Ltd.) in which 50 parts by weight of the modified polyolefin (A1) obtained in Example 1 and 50 parts by weight of low-density polyethylene (NUC-8008 manufactured by Nippon Unicar Co., Ltd.) were set at a temperature of 200 ° C. Kneading was carried out using a product name “Laboplast Mill” manufactured by Toyo Seiki Co., Ltd. to obtain an adhesive resin (B2). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Comparative Example 4)
25 parts by weight of random polypropylene (manufactured by Prime Polymer Co., Ltd .: S235WC), 25 parts by weight of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), hydrogenated styrene thermoplastic elastomer (manufactured by JSR Co., Ltd .: DYNARON 1321P) ) 50 parts by weight of the mixture (a) and (b) 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 minute half-life 175 ° C.) 0.4 A weight part was supplied to a twin-screw extruder (46 mmφ, L / D = 60, manufactured by Kobe Steel, Ltd., product name HYPERKTX46) set at a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm, and melt-kneaded to obtain pellets. After melt-kneading, add 4 parts by weight of glycidyl methacrylate and 4 parts by weight of styrene from the middle of the cylinder. To obtain a sexual polyolefin (B3).

(Comparative Example 5)
25 parts by weight of the modified polyolefin (A1) obtained in Production Example 1 above, 25 parts by weight of high-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUCG-5641), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd.): 50 parts by weight of Tuftec H1221) were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (B4). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Comparative Example 6)
50 parts by weight of the modified polyolefin (A1) obtained in Production Example 1 above, 25 parts by weight of low density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC-8008), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd.): 25 parts by weight of Tuftec H1221) were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (B5). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Comparative Example 7)
25 parts by weight of the modified polyolefin (A1) obtained in Production Example 1 above, 25 parts by weight of polypropylene (manufactured by Prime Polymer Co., Ltd .: S235WC), hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Co., Ltd .: Tuftec H1221) 50 Weight parts were kneaded with a resin kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 200 ° C. to obtain an adhesive resin (B6). The adhesive strength and tensile elastic modulus were measured by the following methods.

(Adhesive strength measurement)
The adhesive resin created in Examples 1 to 5 and Comparative Examples 1 to 7 was sandwiched between two PET films (150 mm × 150 mm × 0.05 mm), and a heating press machine (manufactured by Shindo Metal Industry Co., Ltd .: In a product name compression molding machine NSF-50), a test sample was obtained by bonding under the conditions of a predetermined heating temperature (200 ° C., 5 MPa). This was cut into a width of 10 mm, and T-peel strength was measured at 23 ° C. under a tensile test speed of 200 mm / min using an autograph (manufactured by Shimadzu Corporation: AG-2000A).

(Tensile modulus measurement)
In Examples 1-5, a heat press was performed under the conditions of a predetermined heating temperature (200 ° C., 5 MPa) using a heating press machine (manufactured by Shinfuji Metal Industry Co., Ltd .: product name compression molding machine NSF-50). An approximately 1 mm thick sheet of the adhesive resin prepared in Comparative Examples 1 to 7 was obtained. This was cut into the size of mini dumbbell 2 (1/3), and using an autograph (manufactured by Shimadzu Corporation: AG-2000A) at 23 ° C. under a tensile test speed of 50 mm / min. Tensile modulus was measured.

  The results are shown in Table 1. Examples 1-5 used the adhesive resin composition of this invention, and all showed strong adhesive strength. On the other hand, in Comparative Example 1 in which the modified polypropylene alone was used, Comparative Example 2 in which only the modified polypropylene and styrene thermoplastic elastomer were mixed, and Comparative Example 3 in which only the modified polypropylene and low-density polyethylene were mixed, the adhesive strength was low. It was.

  Comparing Example 1 and Comparative Example 2, it is more effective to add a styrene elastomer to a mixture of modified polypropylene and low density polyethylene than to add a styrene thermoplastic elastomer to the modified polypropylene alone. It can be seen that the elastic modulus of the resin can be lowered and contributes to the improvement of the adhesive strength.

  When Example 1 is compared with Comparative Example 5 and Comparative Example 7, when high-density polyethylene or polypropylene is added instead of low-density polyethylene, the tensile elastic modulus of the resin composition is not sufficiently lowered, and adhesion is also improved. I understand that it is scarce.

  Further, the comparative example 6 which is outside the range of 0.7 <C / (A + B) <1.1 also showed a low T-peel strength. This is because the tensile elastic modulus was not sufficiently lowered due to the relatively small addition amount of the styrene elastomer.

(Processability)
When Example 1 and Comparative Example 4 are compared, the tensile modulus and T-peel strength are good, but since the crosslinking reaction of the styrene elastomer and / or low density polyethylene proceeds during melt modification, the melt viscosity is remarkably high. As a result, the resin became poor in moldability.

Claims (5)

An adhesive comprising a modified polyolefin (A) having a tensile elastic modulus of 500 MPa or more and 1500 MPa or less, a low density polyethylene or linear low density polyethylene (B) having a density of 0.940 g / cm ³ or less, and a styrenic thermoplastic elastomer (C). A functional resin composition comprising:
The weight ratio of each component is 0.7 <C / (A + B ) <1.1, the tensile modulus of the adhesive resin composition Ri der below 100 MPa,
The modified polyolefin (A) is produced by a modification step in which a polyolefin, an epoxy group-containing vinyl monomer and an aromatic vinyl monomer are melt-kneaded in the presence of a radical polymerization initiator. parts with respect to the epoxy group-containing vinyl monomer is added 0.1 to 20 parts by weight adhesive resin composition characterized by degeneration to Rukoto. The resin composition according to claim 1 , wherein the epoxy group-containing vinyl monomer is a methacrylic acid ester or an acrylic acid ester containing an epoxy group, or a derivative thereof. The resin composition according to claim 1 , wherein the aromatic vinyl monomer is styrene or a derivative thereof. The styrenic thermoplastic elastomer (C) was selected from a styrene-isoprene block copolymer, a styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, a hydrogenated styrene-butadiene block copolymer, and a hydrogenated styrene-butadiene random copolymer. characterized in that at least one claim 1-3 Neu resin composition deviation crab according. A layer of a thermoplastic resin comprising at least one selected from the group consisting of polyolefin resins, styrene resins, polycarbonate resins, acrylic resins , polyamide resins, polyphenylene ether resins and polyester resins. The laminated body formed by adhere | attaching with the at least 1 resin composition in any one of 1-4 .