Active energy ray curable adhesive composition and its laminate

Abstract

The objective is to provide an active energy ray-curable adhesive composition that exhibits excellent adhesion to olefin-based materials (substrates and laminates) under thin film and low energy conditions, and a laminate using the same. [Solution] An active energy ray-curable adhesive composition comprising (A) a resin, (B) an ethylenically unsaturated monomer, and (C) a photoinitiator, wherein the total amount of (A) resin is 10 to 45% by mass of 100% by mass of the active energy ray-curable adhesive composition, and the (A) resin contains 20 to 80% by mass of chlorinated polyolefin resin of 100% by mass of the (A) resin, and a laminate using the same.

Description

[Technical Field]

[0001] This invention relates to an active energy ray-curable adhesive composition suitable for bonding polymer materials and the like, and a laminate using the same. More specifically, it relates to an active energy ray-curable adhesive composition that has excellent workability, coating and printability, and exhibits excellent adhesion to polymer materials and the like, particularly to polyolefin materials such as PE (polyethylene) and PP (polypropylene), which are difficult to bond, as well as excellent resistance to moisture and heat, in a thin film and with low energy requirements, and to a laminate using the same. [Background technology]

[0002] Adhesive compositions are widely used in various fields, including packaging materials, labeling materials, building materials, electronic components, and optical components. Conventional solvent-curing adhesive compositions have poor productivity due to the time required for solvent drying, and also pose environmental challenges such as the generation of VOCs (volatile organic compounds) and CO2 emissions. Therefore, adhesive compositions that cure with active energy rays such as electron beams and ultraviolet rays are increasingly being used. These active energy ray-curable adhesive compositions can generally be used without solvents and can be cured in a short time with little energy, thus offering excellent properties from the standpoint of improving productivity and reducing environmental impact.

[0003] On the other hand, as the fields and applications of active energy ray-curable adhesive compositions expand, and as performance improvements and cost reductions progress, there is a growing demand for adhesive compositions that can be thinned, cured with low energy, and provide sufficient adhesion and heat and humidity resistance.

[0004] As an active energy ray curable adhesive composition, for example, an active energy ray curable adhesive composition containing a polyester resin or a petroleum resin that is solid at room temperature (23°C) and a homopolymer urethane (meth)acrylate with a glass transition temperature (Tg) of less than 30°C has been reported to have excellent adhesion to paper substrates and plastic film substrates under thin film and low energy conditions (see Patent Document 1). In addition, an ultraviolet curable adhesive composition containing 1 to 25% by weight of chlorinated polyolefin, 15 to 59% by weight of a radical polymerizable diluent containing ethylene oxide-modified isocyanurate and monofunctional acrylic monomer, and 40 to 60% by weight of acrylic polymer has been reported to have excellent adhesion to polyolefins such as PE (polyethylene) and PP (polypropylene), which are difficult to adhere to substrates (see Patent Document 2).

[0005] However, while the composition described in Patent Document 1 showed excellent adhesion to materials under thin film and low energy conditions, its adhesion to polyolefin materials such as PE (polyethylene) and PP (polypropylene), which are difficult to adhere to, was insufficient. Furthermore, although the composition described in Patent Document 2 showed sufficient adhesion to polyolefin materials, it suffered from poor curing under thin film and low energy conditions, resulting in insufficient adhesion and resistance to moisture and heat. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 7358721 [Patent Document 2] Patent No. 5533406 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The object of the present invention is to provide an active energy ray curable adhesive composition and a laminate using the same that exhibits excellent adhesion and heat and moisture resistance to olefin materials (substrates and laminates) such as PE (polyethylene) and PP (polypropylene), which are difficult to adhere to, under thin film and low energy conditions. [Means for solving the problem]

[0008] As a result of diligent research to solve the aforementioned problems, the inventors have found that the aforementioned problems can be solved by the following active energy ray curable adhesive composition, and have completed the present invention.

[0009] [1] An active energy ray curable adhesive composition comprising (A) a resin, (B) an ethylenically unsaturated monomer, and (C) a photoinitiator, The total amount of the resin (A) is 10 to 45% by mass of the active energy ray curable adhesive composition by mass. An active energy ray curable adhesive composition wherein the resin (A) contains 20 to 80% by mass of chlorinated polyolefin resin in 100% by mass of the resin (A).

[0010] [2] The active energy ray curable adhesive composition according to [1], wherein the chlorinated polyolefin resin has a chlorine content of 30% by mass or more.

[0011] [3] The active energy ray curable adhesive composition according to [1] or [2], wherein the (A) resin further comprises at least one selected from the group consisting of rosin resin, petroleum resin, phenol resin, terpene resin, and xylene resin.

[0012] [4] The active energy ray curable adhesive composition according to [3], wherein the mass ratio of the chlorinated polyolefin resin to the total amount of rosin resin, petroleum resin, phenol resin, terpene resin, and xylene resin is 10 / 90 to 80 / 20.

[0013] [5] The active energy ray curable adhesive composition according to any one of [1] to [4] above, wherein the chlorinated polyolefin resin is a chlorinated polypropylene resin.

[0014] [6] (B) The active energy ray curable adhesive composition according to any one of [1] to [5] above, wherein the total amount of the difunctional or higher functional monomers in the active energy ray curable adhesive composition is 2% by mass or less in 100% by mass of the active energy ray curable adhesive composition.

[0015] [7] The active energy ray curable adhesive composition according to any one of [1] to [6] above, which is for olefinic materials.

[0016] [8] The active energy ray curable adhesive composition according to any one of [1] to [7] above, which is used in a wet lamination method.

[0017] [9] A printed matter obtained by printing the active energy ray curable adhesive composition according to any one of [1] to [8] above on a substrate.

[0018]

[10] A laminate having an adhesive layer formed by curing the active energy ray curable adhesive composition according to any one of [1] to [8] above on a substrate and a laminate material.

[0019]

[11] A method for producing a laminate, wherein the active energy ray curable adhesive composition according to any one of [1] to [8] above is applied or printed on a substrate, a laminate material is laminated on the applied or printed surface, and an active energy ray is irradiated to cure the adhesive layer.

Advantages of the Invention

[0020] According to the present invention, it is possible to provide an active energy ray-curable adhesive composition having excellent adhesiveness and wet heat resistance to olefin-based materials such as difficult-to-adhere PE (polyethylene) and PP (polypropylene) even under thin film and low energy amount conditions, and a laminate using the same. Further, according to the present invention, it is possible to provide an active energy ray-curable adhesive composition having better storage stability, coating, and printing suitability, and a laminate using the same.

Embodiments for Carrying Out the Invention

[0021] Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

[0022] In the following description, (meth)acrylate, (meth)acryloyl, and meth(acrylic) mean methacrylate and / or acrylate, methacryloyl and / or acryloyl, and methacryl and / or acrylic, respectively.

[0023] The active energy ray-curable adhesive composition of the present invention contains (A) a resin, (B) an ethylenically unsaturated monomer, and (C) a photoinitiator, and the total amount of the (A) resin is 10 to 45% by mass in 100% by mass of the active energy ray-curable adhesive composition, and the (A) resin contains a chlorinated polyolefin resin in an amount of 20 to 80% by mass in 100% by mass of the (A) resin. When the chlorinated polyolefin resin is within the above range, the adhesiveness to the substrate becomes good.

[0024] The content of the (A) resin is 10 to 45% by mass in the total mass of the active energy ray-curable adhesive composition, preferably 15 to 40% by mass, and more preferably 20 to 35% by mass. When the content of the (A) resin is within the above range, the adhesive composition is excellent in coating / printing suitability and adhesiveness.

[0025] The active energy ray curable adhesive composition of the present invention contains 20 to 80% by mass of chlorinated polyolefin resin in the total mass of (A) resin, preferably 30 to 70% by mass, and more preferably 40 to 60% by mass. When the content of chlorinated polyolefin resin in the total mass of (A) resin is within the above range, the adhesive composition has excellent coating and printability and adhesion properties.

[0026] The chlorinated polyolefin resin in the (A) resin contained in the active energy ray curable adhesive composition of the present invention is not particularly limited, but examples include chlorinated resins such as polyethylene, polypropylene, poly-α-olefins such as 1-polybutene, 1-polypentene, and 4-methyl-1-pentene, propylene-α-olefin copolymers (including 1-hexene, cyclohexene, cyclopentene, etc. as α-olefins), propylene-conjugated diene copolymers (including butadiene, pentadiene, isoprene, etc. as conjugated diene α), ethylene-butadiene-propylene copolymers, ethylene-vinyl acetate copolymers, natural rubber, or synthetic isoprene rubber. The chlorine content of the chlorinated polyolefin resin is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. When the chlorine content of the chlorinated polyolefin resin is within the above range, the adhesive composition has good compatibility with (B) ethylenically unsaturated monomers and excellent coating and printing suitability and adhesion.

[0027] Chlorinated polyolefin resins can be synthesized by the following methods. For example, they can be obtained by contacting molecular chlorine with polyolefin in an aqueous suspension or dissolved in a chlorine-based solvent such as carbon tetrachloride or dichloromethane at room temperature to 120°C, without a catalyst, in the presence of a catalyst, under ultraviolet irradiation, at normal pressure, or under pressure.

[0028] (A) Examples of commercially available chlorinated polyolefin resins in the resin include Elastren 302NA-X5 (manufactured by Resonac, chlorinated polyethylene resin, chlorine content 28-31%), Elastren 402NA-X5 (manufactured by Resonac, chlorinated polyethylene resin, chlorine content 35-40% by mass), CE35 (manufactured by Shandong Technological Corporation, chlorinated EVA resin, chlorine content 30-40% by mass), Hardren DX-526P (manufactured by Toyobo MC, chlorinated polypropylene resin, chlorine content 26%), Supercron B (manufactured by Nippon Paper Industries, chlorinated EVA resin, chlorine content 26.5%), Supercron 390 (manufactured by Nippon Paper Industries, chlorinated polypropylene resin, chlorine content 36% by mass), and Supercron 814HS (manufactured by Nippon Paper Industries, chlorinated polypropylene resin, chlorine content 41% by mass). Among these, (B) chlorinated polypropylene resin is preferred from the viewpoint of solubility and adhesion to ethylenically unsaturated monomers, viscosity, and price, and has excellent coating and printing suitability and adhesion. These chlorinated polyolefin resins may be used individually or in combination of two or more types.

[0029] The (A) resin contained in the active energy ray curable adhesive composition of the present invention may include other resins besides the chlorinated polyolefin resin, and examples of resins commonly used in the ink, paint, and adhesive industries can be given. Specifically, examples include (meth)acrylic resin, silicone resin, acrylic silicone resin, polyester resin, fluororesin, rosin resin, petroleum resin, coumarone resin, phenolic resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, terpene resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, vinyl resin, amine resin, ketimine resin, etc. The other resins besides the chlorinated polyolefin resin may be used alone or in combination of two or more. Rosin resin, petroleum resin, phenolic resin, terpene resin, and xylene resin are preferred as they have good adhesion, and rosin resin and petroleum resin are more preferred as they have particularly excellent adhesion at low energy levels.

[0030] Rosin resins are not particularly limited, but examples include unmodified rosin (raw rosin) such as gum rosin, wood rosin, and tall oil rosin, and modified rosin obtained by modifying these unmodified rosins. Modifications in the above modified rosin include, for example, hydrogenation, disproportionation, and polymerization. More specifically, the above modified rosin includes hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosin. Furthermore, examples include rosin ester resins obtained by esterifying the above rosin resin with alcohols, unsaturated fatty acid modified rosin resins obtained by modifying rosin ester resin with unsaturated fatty acids, and unsaturated fatty acid modified rosin ester resins obtained by modifying rosin ester resin with unsaturated fatty acids. Among these, hydrogenated rosin ester resins are preferred from the viewpoint of solubility in ethylenically unsaturated monomers, coating and printing suitability, and adhesion.

[0031] Examples of commercially available rosin resins include Hyper CH-B (manufactured by Arakawa Chemical Industries, hydrogenated rosin resin), Harimac R-80 (manufactured by Harima Chemicals, rosin ester resin), Estergum AA-L (manufactured by Arakawa Chemical Industries, rosin ester resin), Pencel AZ (manufactured by Arakawa Chemical Industries, rosin ester resin), Haritac FK-100 (manufactured by Harima Chemicals, disproportionate rosin ester resin), Pine Crystal KR-85 (manufactured by Arakawa Chemical Industries, hydrogenated rosin resin), Pine Crystal KR-616 (manufactured by Arakawa Chemical Industries, hydrogenated rosin resin), Pine Crystal KE-100 (manufactured by Arakawa Chemical Industries, hydrogenated rosin ester resin), and Pine Crystal KE-311 (manufactured by Arakawa Chemical Industries, hydrogenated rosin ester resin). These rosin resins may be used individually or in combination of two or more types.

[0032] Examples of petroleum resins include C5-based petroleum resins, C9-based petroleum resins, C5-based / C9-based petroleum resins, and alicyclic petroleum resins. Among these, C5-based petroleum resins, C9-based petroleum resins, and C5-based / C9-based petroleum resins are preferred from the viewpoint of (B) solubility in ethylenically unsaturated monomers, suitability for coating and printing, and adhesion.

[0033] Examples of commercially available C5-type petroleum resins include Escorets 1202, Escorets 1304, Escorets 1401 (manufactured by ExxonMobil), Wingtack 95 (manufactured by Goodyear Tire & Rubber Company), Quinton K100, Quinton R100, Quinton F100 (manufactured by Nippon Zeon Co., Ltd.), Picotack 95, and Picopal 100 (manufactured by Rika Hercules Co., Ltd.). Examples of commercially available C9-type petroleum resins include Nippon Oil Neopolymer L-90, Nippon Oil Neopolymer 120, Nippon Oil Neopolymer 130, Nippon Oil Neopolymer 140, Nippon Oil Neopolymer 150, Nippon Oil Neopolymer 170S, Nippon Oil Neopolymer 160, Nippon Oil Neopolymer E-100, Nippon Oil Neopolymer E-130, Nippon Oil Neopolymer 130S, Nippon Oil Neopolymer S (manufactured by ENEOS Corporation), and Petcole LX (manufactured by Tosoh Corporation). As for C5-type / C9-type petroleum resins, copolymers of C5-type petroleum resin and C9-type petroleum resin can be used, and examples of commercially available products include Escorets 2101 (manufactured by ExxonMobil Corporation), Quinton G115 (manufactured by Nippon Zeon Corporation), and Harcotac 1149 (manufactured by Rika Hercules Corporation). These can be used individually or in combination of two or more types.

[0034] The ratio of chlorinated polyolefin resin to the total amount of rosin resin, petroleum resin, phenol resin, terpene resin, and xylene resin is preferably 10 / 90 to 80 / 20 by mass ratio, more preferably 20 / 80 to 75 / 25, and even more preferably 30 / 70 to 70 / 30. (A) When the mass ratio of chlorinated polyolefin resin to the total amount of rosin resin, petroleum resin, phenol resin, terpene resin, and xylene resin in the resin is within the above range, good adhesion and heat and humidity resistance are obtained.

[0035] The (B) ethylenically unsaturated monomer contained in the active energy ray curable adhesive composition of the present invention may be a radical polymerizable compound, and examples include monofunctional monomers having α,β-unsaturated double bonds in the molecule and / or bifunctional or polyfunctional monomers, vinyl monomers, allyl monomers, (meth)acrylate monomers, (meth)acrylamide monomers, and other radical polymerizable monomers. These ethylenically unsaturated monomers may be used alone or in combination of two or more types. (B) The ethylenically unsaturated monomer is preferably contained in an amount of 30 to 75% by mass, more preferably 35 to 70% by mass, and even more preferably 40 to 65% by mass, in the total mass of the active energy ray curable adhesive composition. (B) When the content of the ethylenically unsaturated monomer is within the above range, the adhesive composition has excellent coating and printability and adhesion properties.

[0036] Examples of monofunctional ethylenically unsaturated monomers include (alkyl)(meth)acrylates with 1 to 18 carbon atoms, such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, lauryl(meth)acrylate, and stearyl(meth)acrylate; alkylphenols such as butylphenol, octylphenol, and nonylphenoldodecylphenol; (meth)acrylates of ethylene oxide adducts; and isobornyl(meth)acrylate. , cyclohexyl (meth)acrylate, tricyclodecane monomethylol (meth)acrylate and other alicyclic (meth)acrylates, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate Polyalkylene glycol mono(meth)acrylates such as hydroxyl group-containing (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-vinyl Examples include nitrogen atom-containing monomers such as lupyrolidone, N-vinylformamide, and (meth)acryloylmorpholine, phenoxyethyl acrylate, benzyl (meth)acrylate, glycerin mono(meth)acrylate, acrylic acid phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, β-carboxyethyl (meth)acrylate, (meth)acrylate dimer, and ω-carboxy-polycaprolactone mono(meth)acrylate. Monofunctional ethylenically unsaturated monomers are preferable because they significantly reduce the viscosity of active energy ray-curable adhesive compositions and improve the smoothness of coated and printed films. The monofunctional ethylenically unsaturated monomer is preferably present in an amount of 30 to 75% by mass, more preferably 35 to 70% by mass, and even more preferably 40 to 65% by mass, in the total mass of the active energy ray-curable adhesive composition. Having a monofunctional ethylenically unsaturated monomer content within these ranges results in an adhesive composition with excellent coating and printability and adhesion properties.

[0037] Examples of ethylenically unsaturated monomers with two or more functions include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, other alkylene glycol di(meth)acrylates, polyethylene glycol 200 di(meth)acrylate (the number represents the molecular weight), polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, Polyethylene glycol 1000 di(meth)acrylate, other polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, other polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalyl hydroxypivalate di (meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactone di(meth)acrylate, di(meth)acrylate of bisphenol alkylene oxide (2 molar) adduct, glycerin tri(meth)acrylate, di(meth)acrylate of glycerin ethylene oxide (3 molar) adduct, di(meth)acrylate of diglycerin propylene oxide (3 molar) adduct, and other difunctional monomers, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactone tri(meth)acrylate , trifunctional monomers such as tri(meth)acrylate of ethylene oxide (3 molar) adduct of glycerin, di(meth)acrylate of propylene oxide (3 molar) adduct of glycerin, tri(meth)acrylate of ethylene oxide (3 molar) adduct of trimethylolpropane, tri(meth)acrylate of propylene oxide (3 molar) adduct of trimethylolpropane, pentaerythritol tetra(meth)acrylate, pentaerythritol tetracaprolactone tetra(meth)acrylate, diglycerin tetra(meth)acrylate,Examples of four- or more functional monomers include ditrimethylolpropanetetra(meth)acrylate, ditrimethylolpropanetetracaprolactonetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. The amount of bifunctional or more ethylenically unsaturated monomers is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, in the total mass of the active energy ray curable adhesive composition. The adhesive composition exhibits excellent adhesion when the content of bifunctional or more ethylenically unsaturated monomers is within the above range.

[0038] The surface tension of the (B) ethylenically unsaturated monomer contained in the active energy ray curable adhesive composition of the present invention is preferably 25.0 to 38.0 mN / m (25°C), and more preferably 25.0 to 35.0 mN / m (25°C). The (B) ethylenically unsaturated monomer may include any ethylenically unsaturated monomer with a surface tension within the above range, but it is preferably 25% by mass or more, and more preferably 60% by mass or more, relative to the total amount of (B) ethylenically unsaturated monomer. Having the surface tension of the ethylenically unsaturated monomer within the above range results in excellent solubility of chlorinated polyolefin resin, good compatibility of the adhesive composition, and excellent adhesion and storage stability.

[0039] The ratio of nitrogen-containing ethylenically unsaturated monomers in the (B) ethylenically unsaturated monomers contained in the active energy ray curable adhesive composition of the present invention is preferably 1.0 or less, more preferably 0.8 or less, more preferably 0.5 or less, and more preferably 0.4 or less, relative to the total amount of the (A) resin. Having the nitrogen-containing ethylenically unsaturated monomer within the above range suppresses discoloration of the chlorinated polyolefin resin and provides excellent storage stability.

[0040] The content of alicyclic (meth)acrylate is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less in the active energy ray curable adhesive composition. Within this range, there is the advantage of significantly reducing the odor of the active energy ray curable adhesive composition.

[0041] The (C) photoinitiator contained in the active energy ray curable adhesive composition of the present invention generates radicals upon irradiation with active energy rays such as electron beams, ultraviolet rays, and visible light, initiating the crosslinking and polymerization reactions of the (meth)acrylate groups of the (B) ethylenically unsaturated monomer. Examples of photoinitiators include acetophenone-based photoinitiators, alkylphenone-based photoinitiators, benzoin-based photoinitiators, benzophenone-based photoinitiators, and acylphosphine oxide-based photoinitiators. The (C) photoinitiator is preferably contained in an amount of 0.1 to 10% by mass, and more preferably 0.3 to 8% by mass, of the total mass of the active energy ray curable adhesive composition. When the content of the (C) photoinitiator is within the above range, the adhesive composition exhibits excellent curability and adhesion. The photoinitiator may be used alone or in combination of two or more types.

[0042] [Oligomer] The active energy ray curable adhesive composition of the present invention may appropriately contain known oligomers in addition to (A) a resin, (B) an ethylenically unsaturated monomer, and (C) a photoinitiator. Examples include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, polyacrylic (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, amino resin (meth)acrylate, etc. These oligomers may be used individually or in combination of two or more types.

[0043] [Additives] The active energy ray curable adhesive composition of the present invention may contain, in addition to (A) a resin, (B) an ethylenically unsaturated monomer, and (C) a photoinitiator, known additives as appropriate. Examples include polymerization inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, sensitizers, fluorescent whitening agents, curing agents, coupling agents, plasticizers, leveling agents, surface modifiers, defoaming agents, substrate wetting agents, tackifiers, adhesion promoters, antistatic agents, coloring pigments, extender pigments, pigment dispersants, organic solvents, water, and the like.

[0044] [solvent] The active energy ray-curable adhesive composition of the present invention preferably contains substantially no organic solvents or water. "Substantially no" means that the amount of these substances is 3% by mass or less, more preferably 1% by mass or less, relative to the total mass of the active energy ray-curable adhesive composition, and does not impair adhesion or heat and humidity resistance.

[0045] [viscosity] The viscosity of the active energy ray-curable adhesive composition of the present invention at 25°C is preferably 100 to 3000 mPa·s, and more preferably 200 to 2000 mPa·s. A viscosity within this range at 25°C provides an excellent balance between coating / printing suitability and adhesion. The viscosity was measured using a cone-plate viscometer (cone diameter 20 mm, cone angle 1 degree) at 25°C with a shear rate of 100 s. -1 It can be measured with [this method].

[0046] [Coating and Printing Methods] The method for coating and printing the active energy ray-curable adhesive composition of the present invention is not particularly limited, and known methods can be used. Examples include wet coating methods such as spraying, showering, dipping, roll coaters, die coaters, spin coaters, dispensers, inkjet printing, gravure printing, flexographic printing, and screen printing, with roll coaters, gravure printing, and flexographic printing being preferred.

[0047] [Curing method] The method for curing the active energy ray-curable adhesive composition of the present invention is not particularly limited, and known methods can be used. For example, it can be cured by irradiation with alpha rays, gamma rays, electron beams, X-rays, ultraviolet rays, visible light, or infrared rays. Among these, ultraviolet rays and electron beams are preferred, and ultraviolet rays are more preferred. The peak wavelength of the ultraviolet rays is preferably 150 to 450 nm.

[0048] [Ultraviolet Curing Method] The method for curing the active energy ray-curable adhesive composition of the present invention with ultraviolet light is not particularly limited, and known methods can be used. High-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc., that emit light in the wavelength range of 150 to 450 nm can be used. The integrated luminous intensity should be 10 to 3000 mJ / cm². 2 Preferably 30-1000 mJ / cm² 2 Simply irradiate with UV light. After UV irradiation, heating can be performed as needed to improve adhesion. In this specification, "low energy quantity" refers to, for example, 300 mJ / cm³. 2 More preferably 200 mJ / cm² 2 More preferably, 100 mJ / cm² 2 The following is true: 70 mJ / cm 2 The following may also apply. The amount of energy during curing is not particularly limited, but a low amount of energy allows the effects of the present invention to be maximized.

[0049] [Laminated structure] The laminate is obtained by a dry lamination method in which the active energy ray-curable adhesive composition of the present invention is coated or printed onto a substrate, cured by irradiation with active energy rays, and then bonded with a laminate material; or by a wet lamination method in which the active energy ray-curable adhesive composition is coated or printed onto a substrate, bonded with a laminate material without curing, and then cured and bonded by irradiation with active energy rays. The wet lamination method is preferred for obtaining the laminate in terms of adhesive properties. The film thickness when coating or printing the active energy ray-curable adhesive composition is usually preferably 1 to 50 μm, and more preferably 1 to 10 μm. As used herein, a thin film is, for example, 10 μm or less, more preferably 5 μm or less. By having a film thickness of the adhesive composition within this range, the adhesive composition can produce a laminate with excellent adhesion and curability.

[0050] [Base material] The substrate to which the active energy ray-curable adhesive composition of the present invention is coated or printed is not particularly limited, and known materials can be used. Examples include paper, corrugated cardboard, art paper, coated paper, synthetic paper, and plastic films such as PET (polyethylene terephthalate), PVC (polyvinyl chloride), PC (polycarbonate), PE (polyethylene), PP (polypropylene), and OPP (biaxially oriented polypropylene). The active energy ray-curable adhesive of the present invention is particularly useful because it exhibits excellent adhesion to olefin-based substrates such as PE, PP, and OPP, which are generally difficult to adhere to.

[0051] [Olefin-based materials] Examples of olefin-based materials include (co)polymers of α-olefins such as PE (polyethylene), PP (polypropylene), OPP (biaxially oriented polypropylene), polybutene-1, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-diene copolymer, and isobutene-isoprene copolymer; copolymers of α-olefins and conjugated dienes; and various copolymers of α-olefins with other vinyl monomers, such as vinyl esters like vinyl acetate, (meth)acrylic acid, (meth)acrylic acid esters, maleic anhydride, styrene, vinyltrimethoxysilane, and vinylsilanes such as γ-(meth)acryloyloxypropyltrimethoxysilane. PE, PP, and OPP are preferred. Polyolefin-based films, synthetic papers, etc., using these materials are preferred.

[0052] There are no specific requirements regarding the thickness of the base material and laminate material; a thickness of approximately 20 to 200 μm is acceptable. Furthermore, the surface to be coated or printed may be treated with surface treatments such as plasma treatment, corona treatment, or flame treatment. Additionally, the surface may be vapor-deposited with a metal such as aluminum to enhance its aesthetic appeal. Furthermore, the surface may be coated with acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resins.

[0053] [Ink layer] Before coating or printing the active energy ray-curable adhesive composition of the present invention, a known ink composition may be printed onto the substrate to form an ink layer. Examples include inkjet ink compositions, gravure ink compositions, flexographic ink compositions, and screen printing ink compositions. The ink composition may be water-based, organic solvent-based, or UV-curable, but UV-curable is preferred because it improves the adhesion between the layers with the active energy ray-curable adhesive composition. [Examples]

[0054] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0055] [Preparation of an active energy ray-curable adhesive composition: Example 1] (A) As resins, 20% by mass of Superclon 390 (chlorinated polypropylene resin) and 15% by mass of Pine Crystal KE-100 (rosin resin); (B) As ethylenically unsaturated monomers, 15% by mass of NK ester LA (n-lauryl acrylate), 14.5% by mass of Viscoat 192 (phenoxyethyl acrylate), 10% by mass of IBXA (isobornyl acrylate), and 10% by mass of ACMO (4-acryloylmorpholine); (C) As photoinitiators, 2.5% by mass of DAIDO UV-CURE174 (1-hydroxycyclohexyl-phenyl-ketone) and Omnirad A reactive energy ray-curable adhesive composition was prepared by mixing 2.5% by mass of TPO-L (2,4,6-trimethylbenzoylethoxylphenylphosphine oxide), 10% by mass of Artresin UN-7700 (polyester-based urethane acrylate) as an oligomer, and 0.5% by mass of TegoAirex920 as an additive (antifoaming agent). The mixture was then dissolved and mixed by disperser stirring (1000 rpm) while heating at 80°C.

[0056] [Preparation of Active Energy Ray Curable Adhesive Compositions: Examples 2-29, Comparative Examples 1-6] Examples 2-29 and Comparative Examples 1-6 were obtained using the same method as in Example 1, except that the raw materials and quantities listed in Table 1 were changed. Note that the numbers in Table 1 represent mass percentages, and "-" indicates that the ingredient was not included.

[0057] [Table 1-1] [Table 1-2]

[0058] The information for each ingredient in Table 1 is as follows: (A) Resin • Elastrene 402NA-X5: Manufactured by Resonaq, chlorinated polyethylene resin, chlorine content 35-40% by mass • CE35: Manufactured by Shandong Ketian Chemical Industry Co., Ltd., chlorinated EVA resin, chlorine content 30-40% by mass • Supercron 390: Manufactured by Nippon Paper Industries, made from chlorinated polypropylene resin, with a chlorine content of 36% by mass. • Supercron 814HS: Manufactured by Nippon Paper Industries, chlorinated polypropylene resin, chlorine content 41% by mass • Supercron B: Manufactured by Nippon Paper Industries, chlorinated EVA resin, chlorine content 26.5% by mass • Hardlen DX-526P: Manufactured by Toyobo MC Co., Ltd., chlorinated polypropylene resin, chlorine content 26% by mass. • Dianaal BR-105: Manufactured by Mitsubishi Chemical Corporation, acrylic resin • Byron GK-680: Manufactured by Toyobo Co., Ltd., polyester resin • Pine Crystal KE-100: Manufactured by Arakawa Chemical Industries, Ltd., rosin ester resin CLEARON P125: Hydrogenated terpene resin, manufactured by Yasuhara Chemical Co., Ltd. • Petocol LX: Manufactured by Tosoh Corporation, made of petroleum resin. • MEH-7500: Manufactured by Meiwa Kasei Co., Ltd., phenolic resin • Nicanol HP-100: Manufactured by Fudo Co., Ltd., xylene resin (B) Ethylene unsaturated monomers • NK Ester LA: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., n-lauryl acrylate, surface tension 29.3 mN / m (25℃) • Viscoat 192: Manufactured by Osaka Organic Chemical Industry Co., Ltd., phenoxyethyl acrylate, surface tension 38.0 mN / m (25℃) IBXA: Manufactured by Osaka Organic Chemical Industry Co., Ltd., isobornyl acrylate, surface tension 33.0 mN / m (25℃) ACMO: Manufactured by KJ Chemicals, 4-acryloylmorpholin, surface tension 44.6 mN / m (25℃) • TPGDA: Manufactured by Osaka Organic Chemical Industry Co., Ltd., tripropylene glycol diacrylate, surface tension 33.3 mN / m (25℃) (C), photoinitiator. • DAIDO UV-CURE174: Manufactured by Daido Chemical Industries, Ltd., 1-hydroxycyclohexylphenyl ketone • Omnirad TPO-L: Manufactured by IGM, 2,4,6-trimethylbenzoylethoxylphenylphosphine oxide (Other) Oligomers • Art Resin UN-7700: Manufactured by Negami Kogyo Co., Ltd., homopolymer Tg-40℃, polyester-based urethane acrylate • UV-3700B: Manufactured by Mitsubishi Chemical Corporation, homopolymer Tg-6℃, polyether-based urethane acrylate (Other) additives • TegoAirex920: Acrylic-based defoamer manufactured by Evonik.

[0059] The obtained active energy ray-curable adhesive compositions were evaluated using the following method. The evaluation results are shown in Table 2.

[0060] [Table 2-1] [Table 2-2]

[0061] [viscosity] The viscosity of the obtained active energy ray curable adhesive composition was measured using a cone-plate viscometer (cone diameter 20 mm, cone angle 1 degree) at 25°C with a shear rate of 100 s. -1 The surface pressure was measured and its suitability for coating and printing was evaluated. The range of 100-1500 mPa·s is usable, the range of over 1500-3000 mPa·s is usable with heating, and anything above 3000 mPa·s is not suitable for practical use.

[0062] [Storage stability] The obtained active energy ray-curable adhesive composition was stored at 40°C in a dark environment, and its viscosity and appearance were visually evaluated after 3 months. A practical level of 2 or higher was determined. 5: No thickening or discoloration. 4: No thickening agent, slight discoloration present. 3: No thickening, discoloration present. 2: slightly thickened and discolored 1: thickened and discolored

[0063] [Method for Producing Laminate 1] The obtained active energy ray-curable adhesive composition was applied to an easily adherable PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4360) as a base material using a bar coater #3 (adhesive film thickness: about 5 μm). Then, a corona-treated OPP film (manufactured by Futamura Chemical Co., Ltd., FOA-P2) as a laminate material was laminated using a laminating hand roller. Further, ultraviolet rays were irradiated from the laminate material side using a conveyor-type UV irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp, output 80 W / cm, conveyor speed 30 m / min, lamp height 11 cm) to cure the adhesive composition and produce Laminate 1. The integrated light quantity in the UVA region measured with a UV POWER PUCKII manufactured by EIT was 55 mJ / cm 2 is.

[0064] [Method for Producing Laminate 2] The obtained active energy ray-curable adhesive composition was applied to an easily adherable PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4360) as a base material using a bar coater #3 (adhesive film thickness: about 5 μm). Then, a corona-treated OPP film (manufactured by Futamura Chemical Co., Ltd., FOA-P2) as a laminate material was laminated using a laminating hand roller. Further, ultraviolet rays were irradiated from the laminate material side using a conveyor-type UV irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp, output 160 W / cm, conveyor speed 5 m / min, lamp height 11 cm) to cure the adhesive composition and produce Laminate 2. The integrated light quantity in the UVA region measured with a UV POWER PUCKII manufactured by EIT was 660 mJ / cm 2 is.

[0065] [Method for Producing Laminate 3] The obtained active energy ray-curable adhesive composition was printed onto a substrate, PP-based synthetic paper (Yupo Corporation, IHC75), using a flexographic printing test machine (Matsuo Sangyo Co., Ltd., anilox roll 200 L / INCH, printing speed 30 m / min) (adhesive film thickness approximately 4 μm). Then, a corona-treated OPP film (Futamura Chemical Co., Ltd., FOA-P2), which was used as a laminate material, was bonded to the laminate using a hand-operated laminating roller. Furthermore, ultraviolet light was irradiated from the laminate side using a conveyor-type UV irradiation device (I-Graphics Co., Ltd., high-pressure mercury lamp, output 80 W / cm, conveyor speed 30 m / min, lamp height 11 cm) to cure the adhesive composition and produce laminate 3. The integrated light intensity in the UVA region measured with EIT's UV POWER PUCK II was 55 mJ / cm². 2 That is the case.

[0066] [Method for fabricating laminate 4] The obtained active energy ray-curable adhesive composition was printed onto a substrate, PP-based synthetic paper (Yupo Corporation, IHC75), using a flexographic printing test machine (Matsuo Sangyo Co., Ltd., anilox roll 200 L / INCH, printing speed 30 m / min) (adhesive film thickness approximately 4 μm). Subsequently, a corona-treated OPP film (Futamura Chemical Co., Ltd., FOA-P2), which was the laminating material, was bonded to the laminate using a hand-operated laminating roller. Furthermore, ultraviolet light was irradiated from the laminating material side using a conveyor-type UV irradiation device (I-Graphics Co., Ltd., high-pressure mercury lamp, output 160 W / cm, conveyor speed 5 m / min, lamp height 11 cm) to cure the adhesive composition and produce laminate 4. The integrated light intensity in the UVA region measured with EIT's UV POWER PUCK II was 660 mJ / cm². 2 That is the case.

[0067] [Adhesiveness] The prepared laminate was cut into 100mm x 25mm pieces to create five test specimens. The test was conducted according to the JIS K6854-3 test method using a tensile testing machine (peel speed 200mm / min, 25mm). A 180-degree peel test was performed using (°C, 40% RH). Adhesion was evaluated from the average peel strength obtained from five test specimens. The evaluation criteria are as follows. A practical level is 3 or higher. 5: Average peel strength of 10.0 N / 25 mm or higher 4. Average peel strength of 7.5 N / 25 mm or higher, and less than 10.0 N / 25 mm. 3: Average peel strength of 5.0 N / 25 mm or higher, and less than 7.5 N / 25 mm. 2: Average peel strength of 2.5 N / 25 mm or more, and less than 5.0 N / 25 mm. 1: Average peel strength less than 2.5 N / 25 mm

[0068] [Heat and moisture resistance] The fabricated laminates were left to stand for 168 hours and 360 hours in a small environmental test chamber (ESPEC SH242, 60°C, 90%RH), and then their appearance and adhesion were evaluated. The evaluation criteria are as follows. A practical level is 3 or higher. 5:360 hours, no abnormalities. 4: No abnormalities observed after 168 hours / Minor changes in appearance and adhesion observed after 360 hours. 3: After 168 hours, there were minor changes in appearance and adhesion (at a practical level). 2:168 hours later, abnormalities such as blistering, whitening, and decreased adhesion were observed. 1:168 hours later, delamination (peeling)

[0069] As shown in Table 2, the active energy ray-curable adhesive compositions of Examples 1 to 29 exhibited excellent storage stability, and even under thin film and low energy conditions, laminates using the active energy ray-curable adhesive compositions of Examples 1 to 29 were able to obtain excellent adhesion and resistance to moisture and heat.

Claims

1. An active energy ray curable adhesive composition comprising (A) a resin, (B) an ethylenically unsaturated monomer, and (C) a photoinitiator, The total amount of the resin (A) is 10 to 45% by mass of the active energy ray curable adhesive composition, An active energy ray curable adhesive composition wherein the resin (A) contains 20 to 80% by mass of chlorinated polyolefin resin in 100% by mass of the resin (A).

2. The active energy ray curable adhesive composition according to claim 1, wherein the chlorinated polyolefin resin has a chlorine content of 30% by mass or more.

3. The active energy ray curable adhesive composition according to claim 1, wherein the resin (A) further comprises at least one selected from the group consisting of rosin resin, petroleum resin, phenol resin, terpene resin, and xylene resin.

4. The active energy ray curable adhesive composition according to claim 3, wherein the mass ratio of the chlorinated polyolefin resin to the total amount of rosin resin, petroleum resin, phenol resin, terpene resin, and xylene resin is 10 / 90 to 80 / 20.

5. The active energy ray curable adhesive composition according to claim 1, wherein the chlorinated polyolefin resin is a chlorinated polypropylene resin.

6. The active energy ray curable adhesive composition according to claim 1, wherein the total amount of the ethylenically unsaturated monomer (B) is 2% by mass or less in 100% by mass of the active energy ray curable adhesive composition.

7. The active energy ray curable adhesive composition according to claim 1, for use with olefin-based materials.

8. The active energy ray curable adhesive composition according to claim 1, used in a wet lamination method.

9. A printed article obtained by printing the active energy ray-curable adhesive composition according to any one of claims 1 to 8 onto a substrate.

10. A laminate comprising a substrate, an adhesive layer formed by curing an active energy ray curable adhesive composition according to any one of claims 1 to 8, and a laminate material.

11. A method for manufacturing a laminate, comprising coating or printing an active energy ray-curable adhesive composition according to any one of claims 1 to 8 onto a substrate, laminating a laminate material onto the coated or printed surface, and curing the adhesive layer by irradiation with active energy rays.

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