Adhesive resin composition, single-layer film made from the adhesive resin composition, and laminate

Abstract

To provide an adhesive resin composition which is excellent in extrusion laminate suitability such as roll release and neck-in, exhibits good adhesion to both metallic materials such as SUS, aluminum and copper and organic materials such as polyethylene, polypropylene, polyethylene terephthalate and polyethylene naphthalate, is excellent in heat resistance and cold resistance, and can maintain adhesion even under various environments, a single layer film composed of the adhesive resin composition, and a laminate having an adhesive layer composed of the adhesive resin composition on a base material.SOLUTION: An adhesive resin composition contains 50-99 mass% of specific acid-modified polyolefin (A) and 1-50 mass% of a specific polyester resin (B), in 100 mass% of the adhesive resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive resin composition having excellent adhesion not only to metallic materials such as stainless steel (SUS), aluminum, and copper, but also to organic materials such as polyethylene, polypropylene, and polyethylene terephthalate, a single-layer film made of the adhesive resin composition, and a laminate having an adhesive layer made of the adhesive resin composition on a substrate. [Background technology]

[0002] In recent years, metal and organic materials are sometimes used in combination in solar cell components, automotive components, and building materials. Examples of metal materials include stainless steel (SUS), aluminum, copper, and tinplate, while examples of organic materials include polyethylene, polypropylene, polyethylene terephthalate, and polyethylene naphthalate.

[0003] Patent Document 1 discloses a laminated film in which a sealant layer is laminated on at least one side of a polypropylene film via an adhesive layer, wherein the adhesive layer comprises a mixture of an acid-modified polyolefin resin (A) containing a (meth)acrylic acid ester component and having an unsaturated carboxylic acid component content of 0.01 to 5.0% by weight, and a thermoplastic resin (B) having a glass transition temperature of 5°C or less, and the mass ratio (A) / (B) is in the range of 99 / 1 to 20 / 80.

[0004] Patent Document 2 describes an adhesive resin composition comprising an acid-modified polyolefin resin (A) and a gas-barrier resin (B) as essential components, wherein the density of the acid-modified polyolefin resin (A) is 0.8 to 1.0 g / cm³. 3 The density of the gas-blocking resin (B) is within the range of 1.1 to 1.5 g / cm³. 3 An adhesive resin composition is disclosed, characterized in that the adhesive resin composition contains the gas barrier resin (B) in an amount of 10 to 40 parts by weight per 100 parts by weight of total solids.

[0005] However, the adhesive resin compositions proposed in Patent Documents 1 and 2 had problems with heat resistance and adhesion. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-226870 [Patent Document 2] Japanese Patent Publication No. 2021-143283 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Therefore, the object of the present invention is to provide an adhesive resin composition that exhibits excellent suitability for extrusion lamination such as roll release and neck-in, shows good adhesion to both metallic materials such as SUS, copper, and aluminum, and organic materials such as polyethylene, polypropylene, polyethylene terephthalate, and polyethylene naphthalate, and further exhibits excellent heat-resistant and cold-resistant adhesion, and can maintain adhesion under various environmental conditions, as well as a single-layer film made of the adhesive resin composition, and a laminate having an adhesive layer made of the adhesive resin composition on a substrate. [Means for solving the problem]

[0008] As a result of diligent research, the inventors have found that the above problems can be solved by using an acid-modified polyolefin having a specific melting peak temperature and a polyester resin having a specific melting peak temperature in a specific composition ratio, leading to the present invention. That is, the present invention relates to the following [1] to [4].

[0009] [1] An adhesive resin composition comprising 50 to 99% by mass of an acid-modified polyolefin (A) and 1 to 50% by mass of a polyester resin (B) in 100% by mass of the adhesive resin composition, wherein the melting peak temperature of the acid-modified polyolefin (A) in DSC is 85°C to 130°C, and the melting peak temperature of the polyester resin (B) in DSC is 70°C to 210°C.

[0010] [2] The adhesive resin composition according to [1], wherein the melt mass flow rate measured in accordance with JIS K 7210-1 at a temperature of 190°C and a load of 2.16 kg is in the range of 1 to 100 g / 10 min.

[0011] [3] A single-layer film made of the above adhesive resin composition.

[0012] [4] A laminate having an adhesive layer made of the above adhesive resin composition on a substrate. [Effects of the Invention]

[0013] The present invention provides an adhesive resin composition that exhibits excellent suitability for extrusion lamination, such as roll release and neck-in, and good adhesion to both metallic materials such as SUS, aluminum, and copper, and organic materials such as polyethylene, polypropylene, polyethylene terephthalate, and polyethylene naphthalate, and further exhibits excellent heat-resistant and cold-resistant adhesion, and can maintain adhesion under various environmental conditions; a single-layer film made of the adhesive resin composition; and a laminate having an adhesive layer made of the adhesive resin composition on a substrate. [Modes for carrying out the invention]

[0014] The present invention will now be described in detail. It goes without saying that other embodiments are also included within the scope of the present invention, as long as they are consistent with the spirit of the invention. In this specification, numerical ranges specified using "~" include the numbers before and after "~" as the lower and upper limits. In this specification, neck-in refers to a phenomenon in an extrusion laminator where the width of the film of the adhesive resin composition discharged in a film form from a die is narrower than the width of the die, and the larger the neck-in, the inferior the extrusion lamination suitability.

[0015] <Acid-modified polyolefin (A)> The melting peak temperature of the acid-modified polyolefin (A) in DSC is 85°C or higher and 130°C or lower. It is necessary to set the melting peak temperature of the acid-modified polyolefin within a predetermined range in order to exhibit adhesiveness, heat-resistant adhesiveness, and cold-resistant adhesiveness. If it is outside the range, the above effects cannot be expressed.

[0016] The melting peak temperature of the acid-modified polyolefin (A) in DSC is preferably in the range of 90°C or higher and 125°C, more preferably in the range of 100°C or higher and 120°C or lower, and particularly preferably in the range of 105°C or higher and 115°C or lower. The melting peak temperature in this specification is the temperature at the apex of the endothermic peak measured at a heating rate of 10°C / min in accordance with JIS K 7121:1987.

[0017] The method for producing the acid-modified polyolefin is not particularly limited. For example, there is a method of grafting an α,β-unsaturated carboxylic acid or its anhydride to a polyolefin as a base polymer in a molten state in the presence of a radical initiator, as described in JP-A-11-335427. These acid-modified polyolefins (A) may be used alone or in combination of two or more.

[0018] The types of monomer constituting the acid-modified polyolefin (A) are not particularly limited. For example, ethylene, propylene, 1-butene, 1-octene, 4-methylpentene-1, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, isooctyl (meth)acrylate, glycidyl (meth)acrylate, dimethyl maleate, diethyl maleate, vinyl acetate, vinyl propionate, tetracyclododecene, etc. may be mentioned. It may be a single polymer composed of these alone or a multi-component polymer composed of a plurality of them.

[0019] The acid component of the acid-modified polyolefin is not particularly limited, and examples include maleic acid, acrylic acid, methacrylic acid, itaconic acid, etc. Among these, maleic acid is preferably used. Also, acid anhydrides, acid esters, acid amides, acid halides, etc., which are derivatives of these, may be mentioned. Among these, acid anhydrides are preferred.

[0020] The density of the acid-modified polyolefin (A) is preferably in the range of 0.85 to 1.0 g / cm 3 and more preferably in the range of 0.86 to 0.98 g / cm 3 and particularly preferably in the range of 0.88 to 0.95 g / cm 3 in the range.

[0021] The melt mass flow rate (hereinafter referred to as MFR) of the acid-modified polyolefin (A) is preferably in the range of 1 to 100 g / 10 min, more preferably in the range of 2 to 50 g / 10 min, and even more preferably in the range of 5 to 20 g / 10 min. The melt mass flow rate in this specification is the outflow amount for 10 minutes measured under the conditions of 190 °C and a load of 2.16 kg in accordance with JIS K 7210-1:2014.

[0022] <Polyester resin (B)> In the present invention, the polyester resin (B) has a melting peak temperature in DSC of 70°C or higher and 210°C or lower. If the melting peak temperature is below 70°C, the heat resistance and adhesive properties of the adhesive resin composition are insufficient, and if the melting peak temperature is above 210°C, the adhesive properties of the adhesive resin composition are insufficient.

[0023] The melting peak temperature of polyester resin (B) in DSC is preferably in the range of 80 to 190°C, more preferably in the range of 90 to 170°C, and particularly preferably in the range of 100 to 150°C, in terms of adhesion, heat resistance, and cold resistance.

[0024] The dicarboxylic acid and diol components constituting the polyester resin (B) are not particularly limited. Examples of dicarboxylic acids include oxalic acid, succinic acid, glutanoic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. Examples of diols include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol, and 1,3-cyclohexanedimethanol.

[0025] The density of polyester resin (B) is preferably 1.10 to 1.40 g / cm³. 3 The range is, more preferably, 1.12 to 1.30 g / cm³. 3 The range is, and particularly preferably, 1.15 to 1.26 g / cm³. 3 It is within the range of [the specified range].

[0026] The melt viscosity of the polyester resin (B) at 200°C is preferably in the range of 100 to 10,000 dPa·s, more preferably in the range of 500 to 5,000 dPa·s, and even more preferably in the range of 1,000 to 3,000 dPa·s.

[0027] ≪Adhesive resin composition≫ The adhesive resin composition of the present invention contains 50 to 99% by mass of acid-modified polyolefin (A) and 1 to 50% by mass of polyester resin (B) per 100% by mass of the adhesive resin composition. If the content of acid-modified polyolefin (A) is less than 50% by mass, roll release properties tend to be poor and neck-in becomes large, while if it exceeds 99% by mass, adhesion is insufficient. Similarly, if the content of polyester resin (B) is less than 1% by mass, adhesion is insufficient, while if it exceeds 50% by mass, roll release properties tend to be poor and neck-in becomes large.

[0028] The content of the above components (A) and (B) is preferably 60-95% by mass for acid-modified polyolefin (A) and 5-40% by mass for polyester resin (B), more preferably 70-90% by mass for acid-modified polyolefin (A) and 10-30% by mass for polyester resin (B), and most preferably 75-85% by mass for acid-modified polyolefin (A) and 15-25% by mass for polyester resin (B). When the content of acid-modified polyolefin (A) and polyester resin (B) is within the above range, an adhesive resin composition can be obtained that exhibits excellent extrusion lamination suitability such as roll release and neck-in, good adhesion to both metallic materials such as SUS, aluminum, and copper, and organic materials such as polyethylene, polypropylene, polyethylene terephthalate, and polyethylene naphthalate, and further exhibits excellent heat-resistant and cold-resistant adhesion, and can maintain adhesion under various environmental conditions, as well as laminates and adhesive resin composition films using the adhesive.

[0029] The melt mass flow rate of the adhesive resin composition of the present invention is preferably in the range of 1 to 100 g / 10 min, more preferably in the range of 1 to 50 g / 10 min, and particularly preferably in the range of 2 to 20 g / 10 min. A melt mass flow rate of 1 g / 10 min or more is preferable from the viewpoint of sealing properties, and a melt mass flow rate of 100 g / 10 min or less is preferable because it has excellent suitability for extrusion lamination and makes film formation easier.

[0030] The adhesive resin composition may contain additives such as colorants, anti-blocking agents, and antioxidants, to the extent that they do not impair the effects of the present invention. Examples of coloring agents include titanium dioxide. Examples of antiblocking agents include silicones, unsaturated fatty acid amides such as erucic acid amide and oleic acid amide, and saturated fatty acid amides such as stearic acid amide and behenic acid amide. Examples of antioxidants include high molecular weight hindered polyhydric phenols, triazine derivatives, high molecular weight hindered phenols, dialkylphenol sulfides, 2,2-methylene-bis-(4-methyl-6-tert-butylphenol), 4,4-methylene-bis-(2,6-di-tert-butylphenol), 2,6-di-tert-butylphenol-p-cresol, 2,5-di-tert-butylhydroquinone, 2,2,4-trimethyl-1,2-dihydroquinone, 2,2,4-trimethyl-1,2-dihydroquinone, nickel dibutyldithiocarbamate, 1-oxy-3-methyl-4-isopropylbenzene, 4,4-butylidenebis-(3-methyl-6-tert-butylphenol), and 2-mercaptobenzimidazole.

[0031] <Single-layer film> A single-layer film is a film made from the above-mentioned adhesive resin composition. A single-layer film can be obtained, for example, by inflation molding.

[0032] The thickness of the single-layer film is preferably 3 to 200 μm, more preferably 5 to 100 μm, even more preferably 10 to 50 μm, and particularly preferably 15 to 30 μm. The single-layer film of the present invention can fuse two substrates together by sandwiching it between them and applying heat. For example, it exhibits good adhesion to both metallic materials such as SUS, aluminum, and copper, and organic materials such as polyethylene, polypropylene, and polyethylene terephthalate. Furthermore, it has excellent heat resistance and cold resistance, and can maintain its adhesion under various environmental conditions.

[0033] <Laminate> The laminate of the present invention has an adhesive layer made of the above-mentioned adhesive resin composition on a substrate. The method of forming the adhesive layer is not particularly limited, and it is often applied to the substrate using an extrusion laminator. The adhesive resin composition of the present invention has excellent suitability for extrusion lamination. The surface specifications of the cooling rolls of extrusion laminators vary, including matte, mirror, and intermediate semi-matte and semi-mirror finishes, but the adhesive resin composition of the present invention can exhibit good roll release properties for any surface specification of cooling rolls.

[0034] [Base material] The base material may be a single layer film or sheet made of one type of material, such as polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene naphthalate, acrylic, polycarbonate, polyimide, urethane, polypropylene, or polystyrene; Examples include multilayer films or sheets made of two or more substrates, such as PET / PE, which is made by laminating PET and polyethylene (PE), PET / AL, and PET / AL / PE, which are made by laminating PET and aluminum foil (AL). These substrates may have a vapor-deposited layer of alumina, silica, or the like.

[0035] The thickness of the adhesive layer in the laminate is preferably 3 to 200 μm, more preferably 5 to 100 μm, even more preferably 10 to 50 μm, and particularly preferably 15 to 30 μm.

[0036] As described above, the laminate of the present invention exhibits good adhesion to both metallic materials such as SUS, aluminum, and copper, and organic materials such as polyethylene, polypropylene, and polyethylene terephthalate. Furthermore, it has excellent heat resistance and cold resistance, and can maintain its adhesion under various environmental conditions. [Examples]

[0037] The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of the present invention in any way. Unless otherwise specified, "parts" and "%" in the examples represent "parts by mass" and "mass%", respectively.

[0038] <Acid-modified polyolefin (A)> A-1: Modic F534A manufactured by Mitsubishi Chemical Corporation, MFR 3.5 g / 10 min, melting peak temperature 120 °C, density 0.90 g / cm 3 A-2: Modic L502 manufactured by Mitsubishi Chemical Corporation, MFR 1.0 g / 10 min, melting peak temperature 110 °C, density 0.93 g / cm 3 A-3: Modic A515 manufactured by Mitsubishi Chemical Corporation, MFR 9.5 g / 10 min, melting peak temperature 88 °C, density 0.95 g / cm 3 A-4: Admer SE810 manufactured by Mitsui Chemicals, Inc., MFR 7.2 g / 10 min, melting peak temperature 124 °C, density 0.89 g / cm 3 <Other acid-modified polyolefin (A')> A'-1: Admer QF500 manufactured by Mitsui Chemicals, Inc., MFR 3.0 g / 10 min, melting peak temperature 161 °C, density 0.90 g / cm <No. 3 A'-2: Bondine HX8290 manufactured by Arkema, MFR 65 g / 10 min, melting peak temperature 81 °C, density 1.0 g / cm <No. 3

[0039] <Polyester resin (B)>[[ID=二十九]] B-1: Vyron 200 manufactured by Toyobo Co., Ltd., melting peak temperature 78 °C, specific gravity 1.26, Tg 67 °C B-2: Vyron GA-6400 manufactured by Toyobo Co., Ltd., melting peak temperature 96 °C, specific gravity 1.22, Tg -20 °C B-3: Vyron GM-920 manufactured by Toyobo Co., Ltd., melting peak temperature 107 °C, specific gravity 1.15, Tg -60 °C B-4: Vyron GM-913 manufactured by Toyobo Co., Ltd., melting peak temperature 126 °C, specific gravity 1.15, Tg -70 °C B-5: Byron GA-1300 manufactured by Toyobo Co., Ltd., melting peak temperature 167°C, specific gravity 1.26, Tg -6°C B-6: Byron RN-9300 manufactured by Toyobo Co., Ltd., melting peak temperature 198°C, specific gravity 1.34, Tg -73°C <Other polyester resins (B')> B'-1: Kuraray Co., Ltd.'s Clapet KS710B-8S, melting peak temperature 233℃, density 1.38 g / cm³ 3 Tg 82℃

[0040] <Additives> Antioxidant: Hindered phenol antioxidant Blocking inhibitor: Erucic acid amide

[0041] <Manufacturing of adhesive resin compositions> [Example 1] In a Henschel mixer, 90 parts by mass of acid-modified polyolefin (A) (A-1), 10 parts by mass of polyester resin (B) (B-2), and 0.2 parts by mass each of antioxidant and anti-blocking agent as additives were added and pre-blended for 5 minutes. The pre-blended mixture was then put into a hopper and supplied to a twin-screw extruder using a screw feeder, where it was melt-mixed to produce the adhesive resin composition of Example 1. Twin-screw extrusion melt mixing conditions Twin-screw extruder: IKG PMT32-40.5 Die outlet resin temperature: 120~250℃

[0042] [Examples 2-9, Comparative Examples 1-5] Adhesive resin compositions for Examples 2-9 and Comparative Examples 1-5 were prepared in the same manner as in Example 1, except that the compounding composition (parts by mass) was changed as shown in Table 1.

[0043] <Manufacturing of laminates> Using the obtained adhesive resin composition, the adhesive resin composition was laminated to the PE surface of a PET (thickness 12 μm) / PE (thickness 20 μm) laminated substrate using an extrusion laminator under the following conditions to obtain a laminate with a thickness of 30 μm. Extrusion laminator conditions Extrusion Laminator: Musashino Kikai 400M / M Test EXT Laminator Resin temperature directly beneath the die: 130~270℃ Machining speed: 20m / min T-die width: 300mm Cooling roll surface temperature: 20~25℃

[0044] The following evaluations were performed using the obtained laminate. The results are shown in Table 1.

[0045] [Table 1]

[0046] [Roll release capability] We observed the delamination from the cooling roll during the lamination process and evaluated it according to the following criteria. ○: Peels off easily without any noise (good) △: Peels off from the cooling roll but makes a peeling sound (usable) ×: The laminated film does not detach from the cooling roll and wraps around it (unusable).

[0047] [Neck-in] For each laminate, the laminate width was evaluated according to the following criteria. ○: Lamination width of 250mm or more (good) △: Lamination width of 200mm or more and less than 250mm (usable) ×: Laminating width less than 200mm (not usable)

[0048] [Adhesiveness] Each laminate was cut into 15mm wide strips to prepare test specimens. The test specimens were heat-sealed with SUS (SUS304), aluminum (A1050P), copper (Tough Pitch Copper C1100), high-density polyethylene (HDPE) sheets (Kobe Poly Sheet, manufactured by Showa Denko Materials), unoriented polypropylene (CPP) sheets (Super Pure Ray, manufactured by Idemitsu Unitech), PET sheets (Lumirror, manufactured by Toray), and polyethylene naphthalate (PEN) sheets (Teonex, manufactured by Teijin DuPont Films) at 160°C for 5 seconds under a pressure of 0.3 MPa. After being left for 24 hours at 23°C and 65% relative humidity, the adhesive strength was measured using a tensile strength tester (Autograph AGX-V, manufactured by Shimadzu Corporation) under the conditions of 180° angle peeling and peeling speed of 200 mm / min, and evaluated according to the following criteria. ○: Adhesive strength of 15N / 15mm or higher (good) △: Adhesive strength of 5N / 15mm or more, and less than 15N / 15mm (usable) ×: Adhesive strength less than 5N / 15mm (not usable) [Heat-resistant adhesion] Each laminate was cut into 15 mm wide strips to form test specimens. The test specimens were heat-sealed with the same type of SUS plate, aluminum plate, copper plate, HDPE sheet, CPP sheet, PET sheet, or PEN sheet used in the adhesion evaluation, at 160°C for 3 seconds under a pressure of 0.3 MPa. After being left in an 80°C atmosphere for 1000 hours, the adhesive strength was measured using a tensile strength tester (Shimadzu Autograph AGX-V) under the conditions of 180° angle peeling and peeling speed of 200 mm / min, and evaluated according to the following criteria. ○: Adhesive strength of 15N / 15mm or higher (good) △: Adhesive strength of 5N / 15mm or more, and less than 15N / 15mm (usable) ×: Adhesive strength less than 5N / 15mm (not usable)

[0049] [Cold resistance adhesion] Each laminate was cut into 15 mm wide strips to form test specimens. The test specimens were heat-sealed with the same type of SUS plate, aluminum plate, copper plate, HDPE sheet, CPP sheet, PET sheet, or PEN sheet used in the adhesion evaluation, at 160°C for 3 seconds under a pressure of 0.3 MPa. After being left in a -30°C atmosphere for 1000 hours, the adhesive strength was measured using a tensile strength tester (Shimadzu Autograph AGX-V) under the conditions of 180° angle peeling and peeling speed of 200 mm / min, and evaluated according to the following criteria. ○: Adhesive strength of 15N / 15mm or higher (good) △: Adhesive strength of 5N / 15mm or more, and less than 15N / 15mm (usable) ×: Adhesive strength less than 5N / 15mm (not usable)

[0050] As shown in Table 1, the adhesive resin composition of the present invention, which contains 50-99% by mass of acid-modified polyolefin (A) with a DSC melting peak temperature of 85°C to 130°C and 1-50% by mass of polyester resin (B) with a DSC melting peak temperature of 70°C to 210°C, exhibits not only processability (roll release, neck-in) but also excellent adhesive strength, heat resistance and cold resistance, demonstrating its usefulness as an adhesive resin composition.

Claims

1. The adhesive resin composition contains 60 to 90% by mass of acid-modified polyolefin (A) and 10 to 40% by mass of polyester resin (B) in 100% by mass. The melting peak temperature in DSC of acid-modified polyolefin (A) is between 85°C and 130°C. The polyester resin (B) is characterized in that its melting peak temperature in DSC is 70°C or higher and 210°C or lower. Adhesive resin composition.

2. The adhesive resin composition according to claim 1, wherein the melt mass flow rate, measured in accordance with JIS K 7210-1 at a temperature of 190°C and a load of 2.16 kg, is in the range of 1 to 100 g / 10 min.

3. A single-layer film comprising the adhesive resin composition according to claim 1 or 2.

4. A laminate having an adhesive layer made of the adhesive resin composition described in claim 1 or 2 on a substrate.

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