JP5201816B2 - Adhesive resin composition and adhesive film - Google Patents

Description

  The present invention relates to a resin composition that has no problem of roll release and blocking properties in film formation by extrusion lamination and has excellent adhesion to both polar materials such as aluminum and glass and nonpolar materials such as polyethylene and polypropylene.

  Conventional resin compositions having adhesion to both polar materials such as glass and aluminum and nonpolar materials such as polyethylene and polypropylene include ethylene-unsaturated carboxylic acid copolymers and ethylene-unsaturated ester copolymer kens. Having a polar group, such as a modified product obtained by grafting an unsaturated carboxylic acid or derivative thereof onto an ethylene-α-olefin, or a modified product obtained by grafting an unsaturated carboxylic acid or derivative thereof onto an ethylene-unsaturated ester copolymer In many cases, a resin composition in which a polymer and a tackifying resin are blended is used.

  However, these ethylene polymers require processes such as saponification and grafting and are generally more expensive than general-purpose resins such as polyethylene, ethylene-α / olefin, and ethylene-unsaturated ester copolymer.

  It has been conventionally known that when a tackifying resin having a high acid value is blended with an ethylene polymer such as an ethylene-unsaturated ester copolymer, the adhesion to polar materials such as glass and aluminum is improved. However, when the blending amount of the high acid value tackifying resin is not appropriate or the type of the ethylene polymer is not appropriate, there is a problem in roll release property and blocking property in film formation by extrusion lamination.

  In recent years, there are films having various performances, and there is a demand for adhesive resins that can be applied to these various films and can obtain a laminate strength with no practical problems. In particular, films that can be directly laminated on a metal-deposited metal such as aluminum, metal oxides such as alumina, or inorganic oxides such as silica, and a film on which the adhesive resin is laminated are polar materials such as glass and aluminum, polyethylene, and polypropylene. Those having adhesion to non-polar materials such as are very useful.

  Patent Document 1 discloses an adhesive resin comprising 80 to 99% by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15 to 40% by weight and 1 to 20% by weight of a modified tackifying resin having an acid value of 70 to 300 mgKOH / g. Compositions have been proposed. However, since there is much vinyl acetate content, there exists a problem in roll release property and blocking property in the film formation in extrusion lamination. Furthermore, the acid value of the modified tackifying resin is particularly preferably 90 to 150 mgKOH / g, and when a tackifying resin having an acid value of 200 mgKOH / g or less is used, the adhesiveness to polar materials such as glass and aluminum Is lacking.

Patent Document 2 describes a resin composition in which 50 parts of an acid-modified rosin resin is added to 100 parts of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 19 wt% and an MFR of 15 g / 10 min. In the case of film formation by extrusion lamination, the amount of roll release and blocking are problematic.
JP-A-53-112983 Japanese Patent Laid-Open No. 10-60394

  The present invention provides an inexpensive resin composition that has no problem of roll release or blocking in film formation by extrusion lamination, and has adhesion to both polar materials such as glass and aluminum and nonpolar materials such as polyethylene and polypropylene. The purpose is to provide.

The present invention provides an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 11% by weight of the whole copolymer and a melt flow rate measured in accordance with JISK 7210 of 0.5 g to 100 g / 10 min. 70% to 95% by weight of union (A), and
The present invention relates to an adhesive resin composition comprising 5 to 30% by weight of a tackifier resin (B) having an acid value of 200 to 300 mgKOH / g.

Furthermore, the present invention further includes a tackifier resin (C) having an acid value of 0 to 10 mgKOH / g, and
It is related with the said adhesive resin composition whose total amount of tackifying resin (B) and tackifying resin (C) is 5 to 30 weight% of the whole composition.

  Furthermore, this invention relates to the said adhesive resin composition whose melt flow rate measured based on JISK7210 is 10-100g / 10min.

  Furthermore, this invention relates to the adhesive film formed by laminating | stacking the said adhesive resin composition on the base material with which metal foil was laminated | stacked, or the base material with which any of a metal, a metal oxide, and an inorganic oxide was vapor-deposited. .

  According to the present invention, there is no problem of roll release or blocking in film formation in extrusion lamination, and a resin composition having good adhesion to both polar materials such as metal and glass and nonpolar materials such as polyethylene and polypropylene. Could be provided.

The resin composition in the present invention comprises an ethylene- vinyl acetate copolymer (A), a tackifier resin (B) having an acid value of 200 mgKOH / g to 300 mgKOH / g, and an acid value of 10 mgKOH / g or less as required. A tackifier resin (C).

In the present invention, usually available ethylene - vinyl acetate copolymer (hereinafter sometimes abbreviated as EVA) main belt flow rate of (A) is 0.5 g / 10 min or more 100 g / 10 min or less. Preferably they are 0.5 g / 10min or more and 50 g / 10min or less, More preferably, they are 3g / 10min or more and 10g / 10min or less. The melt flow rate is a flow rate (g / 10 minutes) of 10 minutes at 190 ° C. and a load of 2160 g, measured according to JISK 7210. The vinyl acetate content is 3% by weight or more and 11% by weight or less. Preferably they are 3 to 10 weight%, More preferably, they are 3 to 6 weight%. If the vinyl acetate content is less than 3% by weight, the adhesion is insufficient. When the content is more than 11% by weight, the roll release property becomes poor in the extrusion lamination, and the filmed product is inferior in the blocking property.

  The melt flow rate of the adhesive resin composition in the present invention is 10 g / 10 min or more and 100 g / 10 min or less. Preferably they are 10 g / 10 minutes or more and 50 g / 10 minutes or less, More preferably, they are 10 g / 10 minutes or more and 30 g / 10 minutes or less. When the melt flow rate is 10 g / 10 min or less or 100 g / 10 min or more, film formation by extrusion lamination tends to be difficult.

  The tackifier resin (B) having an acid value of 200 mgKOH / g or more and 300 mgKOH / g or less in the present invention mainly comprises a rosin-based tackifier resin. More preferably, the acid value of the tackifying resin is 200 mgKOH / g or more and 250 mgKOH / g or less. The rosin-based tackifying resin includes raw rosin, hydrogenated rosin, (meth) acrylic acid modified rosin, hydrogenated (meth) acrylic acid modified rosin, maleic acid modified rosin, hydrogenated maleic acid modified rosin, fumaric acid modified rosin, And hydrogenated fumaric acid-modified rosin. More preferred are hydrogenated rosin, hydrogenated (meth) acrylic acid modified rosin, hydrogenated maleic acid modified rosin, and hydrogenated fumaric acid modified rosin. When the acid value is less than 200 mgKOH / g, the adhesion to the polar material becomes insufficient, and when it is more than 300 mgKOH / g, a problem arises in the corrosiveness in the extruder during extrusion lamination. In the present invention, the amount of the tackifier resin (B) having an acid value of 200 mgKOH / g or more and 300 mgKOH / g or less is 5% by weight or more and 30% by weight or less. Preferably, they are 5 weight% or more and 20 weight% or less, More preferably, they are 5 weight% or more and 10 weight% or less.

  In the resin composition of the present invention, sufficient adhesion to a polar material cannot be obtained even if a tackifying resin having an acid value of 200 mgKOH / g or less is used alone. However, when a tackifier resin of 200 mgKOH / g or more and 300 mgKOH / g or less is used in a range of 5 wt% or more and 30 wt% or less, a tackifier resin having an acid value of 10 mgKOH / g or less is 0 wt% or more and 25 wt% or less. Even when used in combination within a range, sufficient adhesion strength to polar materials can be obtained.

  The tackifier resin (C) having an acid value of 10 mgKOH / g or less in the present invention is not particularly limited as long as the acid value is 10 mgKOH / g or less. In general, the tackifying resin (C) has a better roll release property in the extrusion laminate than the tackifying resin (B), and reduces the blending amount of the tackifying resin (B) within a range where sufficient adhesive force is obtained. What is necessary is just to make it the compounding quantity of tackifying resin (C) increase. In general, mention may be made of natural tackifying resins and synthetic tackifying resins. Natural types include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin-glycerin ester, rosin-pentaerythritol ester, terpene resin, aromatic modified terpene resin, terpene phenol resin, hydrogenated Terpene resin and the like.

  Synthetic tackifying resins are aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, copolymer (C5 / C9) petroleum resin, hydrogenated petroleum resin (alicyclic petroleum resin) ), DCPD petroleum resin (alicyclic petroleum resin), pure monomer petroleum resin (styrene, substituted styrene petroleum resin), coumarone-indene resin, alkylphenol resin, xylene resin, and the like. Among these, alicyclic petroleum resins are preferably used.

  In the present invention, the amount of the tackifier resin (C) having an acid value of 10 mgKOH / g or less is 0% by weight or more and 25% by weight or less. Preferably, they are 5 weight% or more and 20 weight% or less, More preferably, they are 10 weight% or more and 15 weight% or less. When the compounding amount of the tackifying resin (C) is 25% by weight or more, sufficient adhesive strength to polar materials such as glass and aluminum cannot be obtained.

  However, the total amount of the tackifying resin (B) and the tackifying resin (C) is preferably 5 to 30% by weight of the entire composition.

  The softening point of the tackifying resin used in the present invention is 60 ° C. or higher and 150 ° C. or lower. Preferably they are 90 degreeC or more and 135 degrees C or less, More preferably, they are 100 degreeC or more and 130 degrees C or less. If it is less than 60 ° C., blocking tends to occur when it is a single layer or a multilayer film, and if it is higher than 150 ° C., it becomes difficult to obtain adhesive strength.

  Various other additives can be used as necessary. For example, coloring agents, antiblocking agents, antioxidants and the like. Examples of the colorant include titanium oxide. Examples of the antiblocking agent include silicone, 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. Antioxidants include high molecular weight hindered polyhydric phenols, triazine derivatives, high molecular weight hindered phenols, dialkyl phenol 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), 2-mercaptobenzimidazole.

  When this adhesive resin is extruded and laminated, it is desirable to laminate directly to a metal, metal oxide, or inorganic oxide, but an anchor coating agent may be used to further improve the laminate strength. However, it is better to use an anchor coating agent other than organic solvent based on environmental considerations in recent years. In addition, the laminate strength can be improved by ozone treatment, corona discharge treatment, flaming treatment, or the like.

The present invention is specifically shown below.
<Method for creating adhesive resin composition>
EVA, tackifying resin and various additives shown in Table 1 were pre-blended for 5 minutes with a Henschel mixer. A pre-blend product was charged into a hopper and supplied to an extruder using a screw feeder to prepare a resin composition.
Extruder; Co-rotating twin screw extruder PMT32-40.5 manufactured by IK Corporation
Barrel temperature: 140 ° C (supply port 100 ° C)
Screw rotation speed: 100rpm
Supply speed: 5 kg / hr

<Method for creating laminated film>
Using an extrusion laminator, the resin composition was laminated on an aluminum foil (35 μm) with a thickness of 30 μm to prepare a laminated film. Possible to make a laminated film: ○, impossible to make a laminated film: ×. The processing conditions are shown below.
Extrusion laminator: 400M / M test EXT laminator die directly under Musashinokikai Resin temperature: 140-240 ° C. (adjusted appropriately by MFR of resin composition)
Processing speed: 30m / min T die width: 400mm
Cooling roll surface temperature: 20 ° C

<Ethylene-unsaturated ester copolymer>
EVA-1: Ultrasen 537 (manufactured by Tosoh Corporation, vinyl acetate content 6%, MFR 8.5 g / 10 min)
EVA-2: Evaate D3010 (manufactured by Sumitomo Chemical Co., Ltd., vinyl acetate content 10%, MFR 6 g / 10 min)
EVA-3: Ultrasen 545 (manufactured by Tosoh Corporation, vinyl acetate content 11%, MFR 9 g / 10 min)
EVA-4: Ultrasen 625 (manufactured by Tosoh Corporation, vinyl acetate content 15%, MFR 14 g / 10 min)
EVA-5: Evaate K2010 (manufactured by Sumitomo Chemical Co., Ltd., vinyl acetate content 25%, MFR 3 g / 10 min)

<Tackifying resin>
TF-1: KE-604 (Arakawa Chemical Industries, acid value 238 mg KOH / g, softening point 127 ° C.)
TF-2: Licarodin F (Rika Finetech, acid value 175 mgKOH / g, softening point 72 ° C.)
TF-3: Tespol 1155 (manufactured by Hitachi Chemical Co., Ltd., acid value 190 mgKOH / g, softening point 135 ° C.)
TF-4: Alcon P-125 (Arakawa Chemical Industries, acid value 0 mg KOH / g, softening point 125 ° C.)
TF-5: FTR6100 (Mitsui Chemicals, acid value 0.1 mgKOH / g or less, softening point 100 ° C.)

<Additives>
Antioxidant: IRGANOX 1010 (Ciba Specialty Chemicals)
Anti-blocking agent: Incross lip C (manufactured by Croda)
<Measurement method of peel strength>
The laminated film cut to a width of 15 mm and each of the aluminum plate, glass plate, HDPE plate, and CPP plate were heat sealed at 140 ° C. × 0.3 MPa × 1 second. After leaving for 24 hours, the adhesive strength was measured with a tensile strength tester at 180 ° angle peeling, a tensile speed of 200 mm / min, and an atmosphere of 23 ° C.-65% RH. 10 N / 15 mm or more: ◯, 5 to 10 N / 15 mm: Δ, 5 N / 15 mm or less: x.
Tensile strength tester: Tensilon RTA-100 manufactured by Orientec

Claims (4)

An ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 11% by weight of the whole copolymer and a melt flow rate measured according to JIS K 7210 of 0.5 g to 100 g / 10 min (A 70-95% by weight, and
An adhesive resin composition comprising 5 to 30% by weight of a tackifier resin (B) having an acid value of 200 to 300 mgKOH / g. Furthermore, it contains a tackifier resin (C) having an acid value of 0 to 10 mgKOH / g, and
The adhesive resin composition according to claim 1, wherein the total amount of the tackifying resin (B) and the tackifying resin (C) is 5 to 30% by weight of the whole composition. Melt flow rate, as measured in accordance with JIS K 7210 is, according to claim 1 or 2 Symbol mounting adhesive resin composition is 10g~100g / 10 min. Adhesion formed by laminating the adhesive resin composition according to any one of claims 1 to 3 on a substrate on which a metal foil is laminated, or on a substrate on which any one of a metal, a metal oxide, and an inorganic oxide is deposited. Sex film.