Active energy ray curable composition, and laminate using the same

Abstract

The object of the present invention is to provide an active energy ray curable composition that provides a non-slip feel when a person touches a printed and cured surface, or when printed surfaces overlap. [Solution] The above problem can be solved by an active energy ray curable composition containing a polyester polyol (A) and a urethane acrylate (B), wherein the urethane acrylate (B) contains a reaction product of a monofunctional ethylenically unsaturated monomer having a hydroxyl group in its molecule and polymeric diphenylmethane diisocyanate.

Description

Technical Field

[0001] The present invention relates to an active energy ray curable composition and a laminate using the same.

Background Art

[0002] In recent years, in the field of packages using a substrate, for the purpose of giving added value such as durability, cosmetic properties, and texture to printed matter, after printing color ink on various substrates, research on applying a coating varnish has been actively conducted. For example, in view of the case when the printed package is displayed at a store, there may be a requirement for imparting texture such as glossiness or matte property. In response to such a requirement, for example, Patent Document 1 discloses an active energy ray curable composition for forming a cured layer excellent in substrate adhesion and matte property (cosmetic property).

[0003] Regarding the added value provided by the coating varnish as described above, research has also been conducted on imparting a tactile sensation assuming actual touch by hand. For example, Patent Document 2 discloses an ultraviolet curable varnish composition that gives a soft touch feeling.

[0004] The imparting of a touch feeling by printing leads to, for example, an improvement in the willingness to purchase by transmitting the image of the package contents, or also contributes as a plastic reduction means that replaces the conventional means of imparting a touch feeling that was expressed by sticking a film. Considering such merits, it is imagined that the demand for touch feeling varies widely regardless of the exemplified soft feeling. Furthermore, from the perspective of imparting a touch feeling, it can be applied to a wide range of fields such as building materials, household appliances, precision instruments, electronic devices, and automotive interiors, not limited to the package field.

[0005] For example, for the demand of wanting to give a glossy feeling or a touch feeling such that the package does not slip off the fingertips when held by hand, it is appropriate to impart a non-slip feeling (a sticky feeling).

[0006] On the other hand, adding functionality is also an important element in the packaging field. For example, when transporting goods by ship or vehicle, providing stacked packages with a non-slip function is effective in preventing package damage and stabilizing quality, and there is a demand for adding functionality through printing. It is presumed that the aforementioned non-slip sensation will be effective in addressing such challenges. The coating varnishes described in Patent Documents 1 and 2 did not achieve non-slip properties. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Patent No. 6919110 [Patent Document 2] Patent No. 7480924 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a printed surface that can be cured by active energy rays that provides a non-slip feel when touched or when printed surfaces overlap, and also maintains a printed appearance. [Means for solving the problem]

[0009] As a result of diligent research to solve the above problems, we have found that the above problems can be solved by the embodiments shown below, and have completed the present invention.

[0010] An active energy ray curable composition according to one aspect of this disclosure is an active energy ray curable composition containing a polyester polyol (A) and a urethane acrylate (B). The urethane acrylate (B) includes a reaction product of a monofunctional ethylenically unsaturated monomer having a hydroxyl group in its molecule and polymeric diphenylmethane diisocyanate.

[0011] An active energy ray curable composition according to one aspect of this disclosure contains no organic solvent or contains 5% by mass or less of the total mass of the composition.

[0012] An active energy ray curable composition according to one aspect of this disclosure contains a photopolymerization initiator.

[0013] An active energy ray curable composition according to one aspect of the present disclosure comprises a hydroxyalkyl (meth)acrylate, wherein the monofunctional ethylenically unsaturated monomer having one hydroxyl group in the molecule.

[0014] In one aspect of the present disclosure, the active energy ray curable composition is characterized in that, in the urethane formation step to obtain the urethane acrylate (B), the ratio (NCO / OH) of the total number of isocyanate groups in polymeric diphenylmethane diisocyanate to the total number of hydroxyl groups in a monofunctional ethylenically unsaturated monomer having one hydroxyl group in its molecule is 0.50 to 1.00.

[0015] An active energy ray curable composition according to one aspect of the present disclosure contains 40 to 80% by mass of the urethane acrylate (B) in the total mass of the composition.

[0016] An active energy ray curable composition according to one aspect of this disclosure has a storage modulus (Er) of 1000 to 2500 MPa and a loss tangent (tanδ) of 0.30 or less in a single cured film obtained by curing the active energy ray curable composition using an active energy ray.

[0017] An active energy ray curable composition according to one aspect of the present disclosure comprises the active energy ray curable composition.

[0018] A coating composition according to one aspect of this disclosure comprises a substrate layer and a coating layer in sequence. The coating layer is formed from the coating composition.

[0019] The laminate according to one aspect of the present disclosure further has a printing layer between a base material layer and a coating layer.

[0020] A method for manufacturing a laminate according to one aspect of the present disclosure is a method for manufacturing a laminate having a base material layer and a coating layer, which includes a step of applying the coating composition onto the base material by screen printing.

Advantages of the Invention

[0021] According to the present invention, it is possible to provide a radiation curable composition that can impart a non-slip feeling (a cuccu feeling) when touching the printed and cured printing surface and also has a good printing appearance.

Embodiments for Carrying Out the Invention

[0022] Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.

[0023] The radiation curable composition of the present invention is a radiation curable composition containing polyester polyol (A) and urethane acrylate (B), characterized in that the urethane acrylate (B) contains a reaction product of a monofunctional ethylenically unsaturated monomer having a hydroxyl group in the molecule and polymeric diphenylmethane diisocyanate. By including these components, both a feeling of sticking to the fingertips due to viscosity and a feeling of repelling the movement of the fingertips due to elasticity are appropriately imparted, and a non-slip feeling is exhibited.

[0024] In the following description, (meth)acrylic and (meth)acrylate mean methacrylic and / or acrylic, methacrylate and / or acrylate, respectively. Further, (meth)acryloyl means methacryloyl and / or acryloyl. In addition, the radiation curable composition may sometimes be simply referred to as a "composition", which is synonymous.

[0025] <Polyester polyol (A)> The polyester polyol (A) used in the present invention is not particularly limited and can be any compound having two or more hydroxyl groups and two or more ester bonds in its molecule, with ester bonds as repeating units. Examples of such polyester polyols include polyester polyols obtained by reacting a carboxyl group component with a polyol, or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone).

[0026] <Polyol> The aforementioned polyol is not particularly limited as long as it is a known polyol, but examples include diols and polyols with three or more functionalities. Examples of the diols include aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3,3'-dimethylolheptane, and 1,4-bis(hydroxymethyl)cyclohesane; ether glycols such as polytetramethylene ether glycol and polyoxyethylene glycol; modified polyetherdiols obtained by ring-opening polymerization of the aliphatic diol with various cyclic ether bond-containing compounds such as ethylene oxide and tetrahydrofuran; lactone-based polyester polyols obtained by polycondensation reactions of the aliphatic diol with various lactones such as lactanoides and ε-caprolactone; and alkylene oxide adducts of bisphenols obtained by adding ethylene oxide or the like to bisphenols such as bisphenol A and bisphenol F.

[0027] Examples of the three- or more functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol; modified polyether polyols obtained by ring-opening polymerization of the aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; and lactone-based polyester polyols obtained by polycondensation reactions of the aliphatic polyol with various lactones such as ε-caprolactone.

[0028] The polyol is preferably a diol. When a diol is used, the cured film has an appropriate viscosity, which improves the feeling of sticking to the fingertips and tends to improve the non-slip feel.

[0029] <Carboxy group component> The carboxyl group component is not particularly limited as long as it is known, and monofunctional carboxylic acids or polycarboxylic acids can be used. Examples of such carboxyl group components include monofunctional carboxylic acids having aromatic rings such as benzoic acid, phenylacetic acid, and 3-phenylpropionic acid; acyclic aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids; and polybasic acids such as dimer acids.

[0030] The carboxyl group component preferably includes a ring structure such as an alicyclic ring or an aromatic ring. When a ring structure is included, the elasticity of the polyester polyol (A) is appropriately expressed, improving the feeling that the cured film resists the movement of the fingertips and tending to improve the non-slip feel.

[0031] The weight-average molecular weight of the polyester polyol (A) is preferably 1000 to 5000, and more preferably 2000 to 3000. If it is 1000 or more, the weight-average molecular weight after curing increases, the elasticity increases, the feeling of the cured film resisting fingertip movement improves, and the non-slip feel tends to improve. If it is 5000 or less, the viscosity of the composition decreases, the leveling during coating improves, and the printed appearance tends to improve. In addition, the smoothness and defoaming properties of the printed surface tend to increase, and the non-slip feel tends to improve.

[0032] The glass transition temperature (Tg) of the polyester polyol (A) is preferably 80 to 120°C, and more preferably 90 to 115°C. Above 80°C, the elasticity of the polyester polyol (A) is appropriately expressed, improving the feeling of the cured film resisting fingertip movement and tending to improve non-slip properties. Below 120°C, the viscosity of the cured film is appropriately imparted, improving the feeling of it adhering to the fingertips and tending to improve non-slip properties. Furthermore, the viscosity of the composition is reduced, tending to improve the printed appearance.

[0033] In the esterification step to obtain the polyester polyol (A), the ratio (OH / COOH) of the total number of hydroxyl groups in the polyol to the total number of carboxyl groups in the carboxyl group component is preferably 1.0 to 2.0, and more preferably 1.1 to 1.5. If it is 1.0 or higher, the viscosity of the composition tends to decrease, and the printed appearance tends to improve. If it is 2.0 or lower, the elasticity of the cured film increases with increasing molecular weight of the polyester polyol (A), improving the feeling that the cured film resists the movement of the fingertips, and improving the non-slip feel.

[0034] The polyester polyol (A) is preferably present in an amount of 5 to 60% by mass of the total mass of the composition, and more preferably in an amount of 30 to 50% by mass. When the amount is 5% by mass or more, the elasticity of the cured film increases, improving the feeling that the cured film resists the movement of the fingertips and tending to improve the non-slip feel. When the amount is 60% by mass or less, the viscosity of the composition decreases, improving leveling during coating and tending to improve the printed appearance. In addition, the smoothness and defoaming properties of the printed surface increase, and tending to improve the non-slip feel.

[0035] <Urethane acrylate (B)> The urethane acrylate (B) used in this invention contains a reaction product of a monofunctional ethylenically unsaturated monomer having a hydroxyl group in its molecule and polymeric diphenylmethane diisocyanate. The inclusion of these components imparts an appropriate viscosity to the cured film, improving the feeling of it sticking to the fingertips and enhancing the non-slip feel.

[0036] The monofunctional ethylenically unsaturated monomer having a hydroxyl group in the molecule preferably includes hydroxyacryl(meth)acrylate, such as 2-hydroxyethyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate. The number of carbon atoms in the alkyl group is preferably 2 to 10 or 2 to 6, and more preferably 2 to 4.

[0037] Commercially available polymeric diphenylmethane diisocyanate can be used. Examples include Wanhua's "WANNATE PM-200," BASF's "Lupranat M20S," "Lupranat M11S," and "Lupranat M5S," and Tosoh's "Millionate MR-200" and "Millionate MR-100." Polymeric diphenylmethane diisocyanate may also be labeled as crude MDI, and may contain 4,4'-diphenylmethane diisocyanate.

[0038] In the urethane formation step to obtain the urethane acrylate (B), the ratio (NCO / OH) of the total number of isocyanate groups in polymeric diphenylmethane diisocyanate to the total number of hydroxyl groups in the monofunctional ethylenically unsaturated monomer having hydroxyl groups in its molecule is preferably 0.50 to 1.00, and more preferably 0.80 to 0.99. When it is 0.50 or higher, the elasticity of the cured film increases with increasing urethane bond concentration in the composition, improving the feeling of the cured film resisting fingertip movement and tending to improve non-slip feel. When it is 1.00 or lower, the viscosity of the composition decreases, improving leveling during coating and tending to improve the printed appearance. In addition, the smoothness and defoaming properties of the printed surface tend to increase, further improving non-slip feel.

[0039] The urethane acrylate (B) is preferably present in an amount of 40 to 80% by mass of the total mass of the composition, and more preferably 45 to 60% by mass. When the amount is 40% by mass or more, the elasticity of the cured film increases with increasing urethane bond concentration in the composition, improving the feeling of the cured film resisting fingertip movement and tending to improve the non-slip feel. When the amount is 80% by mass or less, the viscosity of the composition decreases, improving leveling during coating and tending to improve the printed appearance. In addition, the smoothness and defoaming properties of the printed surface increase, tending to improve the non-slip feel.

[0040] The urethane acrylate (B) used in the present invention may contain, as necessary, other urethane acrylate components in addition to the reaction product of a monofunctional ethylenically unsaturated monomer having a hydroxyl group in its molecule and polymeric diphenylmethane diisocyanate. For example, from the viewpoint of improving non-slip properties, urethane acrylates containing allophanate bonds or nurate bonds can be suitably used. The amount of the urethane acrylate added is preferably 30% by mass or less of the total mass of the composition, within a range that does not inhibit the function of urethane acrylate (B) and does not cause an excessive increase in the viscosity of the composition. Commercially available urethane acrylates can be used, for example, the "EBECRYL" series manufactured by Daicel Ornex.

[0041] The storage modulus (Er) at 25°C of the cured film obtained by curing the composition of the present invention using active energy rays is preferably 1000 to 2500 MPa, and more preferably 1500 to 2000 MPa. When it is 1000 MPa or higher, the elasticity of the cured film increases, improving the feeling that the cured film repels the movement of the fingertips and tending to improve the non-slip feel. When it is 2500 MPa or lower, the viscosity of the cured film is appropriately imparted, improving the feeling that it adheres to the fingertips and tending to improve the non-slip feel. Furthermore, the loss tangent (tanδ) of the cured film at 25°C is preferably 0.01 to 0.30, and more preferably 0.05 to 0.20. When it is 0.30 or less, the elasticity of the cured film increases, improving the feeling that the cured film resists the movement of the fingertips, and tends to improve the non-slip feel. When it is 0.01 or more, the viscosity of the cured film is appropriately imparted, improving the feeling that it adheres to the fingertips, and tends to improve the non-slip feel. The storage modulus (Er) and loss tangent (tanδ) are measured according to JIS K 7244. Specifically, they can be determined, for example, using a dynamic viscoelasticity measuring device (such as the "DVA-200" manufactured by IT Measurement Control Co., Ltd.).

[0042] <Photopolymerization initiator> The active energy ray curable composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator generates radicals upon irradiation with active energy rays such as light, initiating the crosslinking and polymerization reactions of the acrylate groups of the polyfunctional urethane (meth)acrylate and monofunctional ethylenically unsaturated monomer. Suitable photopolymerization initiators include acetophenone-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators, among which acetophenone-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators are preferred. From the viewpoint of appropriately maintaining the hardness of the coating layer formed from the active energy ray curable resin composition, the photopolymerization initiator is preferably contained in an amount of 1 to 10% by mass, more preferably 2 to 7% by mass, and even more preferably 3 to 5% by mass in the total mass of the composition.

[0043] Examples of the acetophenone-based photopolymerization initiators include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2,2-dimethoxy-2-phenylacetophenone.

[0044] Examples of alkylphenone-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0045] Examples of benzoin-based photopolymerization initiators include benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0046] Examples of benzophenone-based photopolymerization initiators include benzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, methyl-o-benzoylbenzoate, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3-dimethyl-4-methoxybenzophenone. Among these, 4-methylbenzophenone is preferred.

[0047] Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone.

[0048] Examples of anthraquinone-based photopolymerization initiators include α-acyloxime esters, benzyl methylbenzoyl formate ("ViaCure 55"), and 2-ethylanthraquinone.

[0049] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Omnirad TPO") and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("IRGACURE 819").

[0050] The aforementioned photopolymerization initiator may be used as one or a combination of two or more.

[0051] <Organic solvents> The composition of the present invention may optionally contain an organic solvent. If an organic solvent is present, it is preferable that the organic solvent constitutes 5% by mass or less of the total mass of the composition, from the viewpoint of improving the printed appearance and protecting the environment. More preferably, it is 3% by mass or less, and even more preferably 1.5% by mass or less. Examples of usable organic solvents include known solvents used in coating varnishes.

[0052] <Additives> The active energy ray curable composition of the present invention may appropriately contain known additives, such as leveling agents, polymerization inhibitors, ultraviolet absorbers, light stabilizers, sensitizers, curing agents, plasticizers, wetting agents, adhesion aids, defoaming agents, antistatic agents, etc., and there are no particular limitations.

[0053] <Manufacturing of Activated Energy Ray Curable Compositions> The active energy ray curable composition can be produced by stirring a polyester polyol (A), a urethane acrylate (B), and a photopolymerization initiator with a disperser or similar device for 30 minutes to 3 hours. If mixing is difficult and viscosity tends to be uneven, a roller mill, ball mill, pebble mill, attritor, sand mill, etc. may be used.

[0054] If the active energy ray-curable composition of the present invention contains air bubbles or unexpectedly coarse particles, these can degrade the quality of the printed material, so it is preferable to remove them by filtration or other means. Conventional known filters can be used.

[0055] <Coating composition> The coating composition of the present invention is a composition for forming a coating layer and has the same constituent elements as the active energy ray curable composition.

[0056] <Manufacturing of laminates> The active energy ray-curable composition of the present invention can be used as a coating composition containing it in the manufacture of laminates. The method of manufacturing the laminate is not particularly limited, but for example, the active energy ray-curable composition can be printed and coated onto a substrate such as paper or film, and then cured to produce a laminate having a substrate layer / coating layer structure. Alternatively, a printed layer made of a printing ink composition may be formed on the substrate, and the coating layer of the present invention may be laminated on the printed layer to form a laminate having a substrate layer / printed layer / coating layer structure.

[0057] The printing and coating methods for the active energy ray curable composition are not particularly limited and include wet coating methods such as spraying, showering, dipping, flow coating, gravure printing, flexographic printing, roll printing, spinning, dispenser printing, inkjet printing, and screen printing. Screen printing is preferred from the viewpoint of easily forming thick films and being able to coat even high-viscosity materials.

[0058] While there are no particular limitations on the screen plates used for screen printing, a narrower mesh size is preferable. A narrower mesh size in the screen plate tends to improve print resolution and thus the appearance of the printed material.

[0059] Examples of active energy rays include ultraviolet rays such as far ultraviolet, ultraviolet, and near ultraviolet rays. On the other hand, electron beams and proton beams can also be used, and in this case curing can be achieved without the use of a photopolymerization initiator, but curing by ultraviolet irradiation is preferred due to the curing speed, ease of obtaining irradiation equipment, and cost.

[0060] Methods of curing by ultraviolet irradiation include using 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 150-450 nm wavelength range, with an integrated light intensity of 30-5000 mJ / cm². 2 Preferably 100-1000 mJ / cm² 2 Simply irradiate it. After UV irradiation, heating can be performed as needed to ensure complete curing.

[0061] The thickness of the coating layer is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 1 to 30 μm. Within this range, smoothness and defoaming properties tend to improve, and a moderate non-slip feel can be provided. In addition, the printed appearance tends to improve.

[0062] <Base material> The substrate used in this invention can be, for example, a paper substrate or a film substrate. For paper substrates, ordinary paper or corrugated cardboard is preferred, and although there are no specific requirements for film thickness, a thickness of 0.2 mm to 1.0 mm is suitably used, and the printed surface may be corona treated. Furthermore, the paper substrate may have its surface vapor-deposited with a metal such as aluminum to enhance its design, and may also be surface coated with acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resins, and may also be further surface treated with corona treatment. For example, coated cardboard and Mariecoat paper are preferred. For film substrates, ordinary PET (polyethylene terephthalate) and PVC (polyvinyl chloride) are suitable, and there are no particular limitations. A film thickness of 0.02 mm to 1.0 mm is preferably used, and the substrate surface may be corona-treated. Furthermore, the film substrate may be surface-coated with acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resins.

[0063] <Printing ink composition> The aforementioned printing ink composition may include, for example, known gravure ink compositions, flexographic ink compositions, UV-curable flexographic ink compositions, offset ink compositions, UV-curable offset ink compositions, and other ink compositions, and any of these printing ink compositions may be used. In particular, when using UV-curable offset ink compositions or UV-curable flexographic ink compositions, if active energy ray-curable compositions are laminated, curing reactions by ultraviolet light or the like occur between the layers, improving adhesion. For this reason, UV-curable offset ink compositions and UV-curable flexographic ink compositions are more preferred as printing ink compositions.

[0064] <Printing with printing ink> Known methods can be used for printing the printing ink composition. Examples include gravure printing, flexographic printing, offset printing, and screen printing. The thickness of the ink layer is preferably 0.1 to 15 μm, and more preferably 0.5 to 12 μm. The printing ink composition may be organic solvent-based, water-based, or an ultraviolet-curable ink composition. Alternatively, the above printing ink compositions may be combined to form the ink layer, which can then be dried or ultraviolet-cured after printing to form the printed layer.

[0065] The thickness of each layer can be measured from the cross-section of the laminate. The method for cutting the cross-section is not particularly limited and can be, for example, a razor, cutter, microtome, or ion milling, and may be performed after cooling with liquid nitrogen or the like. The method for measuring the thickness is not particularly limited and can be, for example, a laser microscope, optical microscope, or electron microscope. [Examples]

[0066] The present invention will be specifically described below with reference to examples and comparative examples. In the examples and comparative examples, "parts" and "%" mean "parts by mass" and "% by mass" respectively, unless otherwise specified.

[0067] [Method for measuring weight-average molecular weight] The weight-average molecular weight was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) instrument (HLC-8220, Tosoh Corporation) and calculating the converted molecular weight using polystyrene as the standard substance. The measurement conditions are shown below. Columns: The following columns were used, connected in series. TSKgelSuperAW2500 manufactured by Tosoh Corporation TSKgel SuperAW3000 manufactured by Tosoh Corporation TSKgel SuperAW4000 manufactured by Tosoh Corporation TSKgelguard Column Super AWH manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Measurement conditions: Column temperature 40°C Eluent: Tetrahydrofuran Flow rate: 1.0mL / min

[0068] [Method for measuring glass transition temperature] The glass transition temperature (Tg) was measured using a DSC (Differential Scanning Calorimetry) system (Rigaku Corporation "DSC8231"). The glass transition temperature was defined as the midpoint between the endothermic onset temperature and the endheating onset temperature based on the glass transition in the DSC curve. The measurement conditions are shown below. Measurement temperature range: -70 to 150°C Heating rate: 10°C / min

[0069] [Method for measuring storage modulus (Er) and loss tangent (tanδ)] The storage modulus (Er) and loss tangent (tanδ) were measured using a dynamic viscoelasticity measuring device (IT Measurement Control Co., Ltd. "DVA-200") in accordance with JIS K 7244. For comparison, values ​​at a measurement temperature of 25°C were used. The measurement conditions are shown below. Frequency: 10Hz Measurement temperature range: -100 to 300°C Heating rate: 10°C / min

[0070] <Manufacturing of polyester polyol (A)> (Synthesis of polyester polyol (A-1)) In a reaction vessel equipped with a stirrer, temperature gauge, reflux condenser, dropping tank, and nitrogen gas inlet, 559.3 parts of phthalic anhydride, 171.4 parts of diethylene glycol, 126.1 parts of neopentyl glycol, and 143.1 parts of 1,6-hexanediol were charged, and the mixture was heated to 240°C while stirring under a nitrogen atmosphere. The reaction was continued until the acid value was 5 mg KOH / g or less, after which the pressure was gradually reduced and the reaction was continued at 1 mmHg to remove excess alcohol and obtain polyester polyol (A-1). The weight-average molecular weight was 2500, and the glass transition temperature was 110°C.

[0071] (Synthesis of polyester polyols (A-2 to A-5)) Polyester polyols (A-2 to A-5) were obtained in the same manner as in (A-1), except that the raw materials were changed to the formulations (parts by mass) listed in Table 1.

[0072] [Table 1]

[0073] <Manufacturing of urethane acrylate (B)> (Synthesis of urethane acrylate (B-1)) In a reaction vessel equipped with a stirrer, temperature gauge, reflux condenser, dropping tank, and nitrogen gas inlet, 520.0 parts of 4-hydroxybutyl acrylate ("4-hydroxybutyl acrylate" manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 480.0 parts of polymeric diphenylmethane diisocyanate ("WANNATE PM-200" manufactured by Wanhua Co., Ltd.) were charged. The reaction was carried out by heating at 80°C to 90°C for 3 hours while stirring under a nitrogen gas stream. After confirming the disappearance of the peaks caused by the isocyanate group by measuring the IR spectrum, the reaction was terminated, and the mixture was cooled to room temperature to obtain urethane acrylate (B-1) as a brown liquid.

[0074] (Synthesis of urethane acrylate (B-2~B-5)) Urethane acrylates (B-2 to B-5) were obtained in the same manner as in (B-1), except that the raw materials were changed to the formulations (parts by mass) listed in Table 2.

[0075] [Table 2]

[0076] Details of Table 2 are shown below. PM-200: Polymeric diphenylmethane diisocyanate (Wanhua Corporation's "WANNATE PM-200") 24A-100: Biuret form of hexamethylene diisocyanate (Asahi Kasei Corporation's "Duranate 24A-100") 2-HEA: 2-Hydroxyethyl acrylate (Hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4-HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd. as "4-Hydroxybutyl acrylate")

[0077] <Manufacturing of Activated Energy Ray Curable Compositions and Coating Layers> (Example 1) A composition curable by active energy rays was obtained by mixing 42 parts of polyester polyol (A-1), 50 parts of urethane acrylate (B-1), 5 parts of the photopolymerization initiator Omnirad 1173, and 3 parts of the defoaming agent, and stirring with a bladed stirrer for 90 minutes. Next, using a screen (300 mesh / inch, polyester resin fiber, mesh opening 45 μm, wire diameter 30 μm, emulsion thickness 10 μm, transmission area 75 mm × 50 mm, theoretical coating thickness 38 μm), the active energy ray curable composition was applied onto an easily adhesive PET substrate (Toyobo Co., Ltd.'s "Cosmoshine A4160") and cured with a UV lamp to form a coating layer, thereby obtaining a laminate consisting of a substrate and a coating layer. The UV lamp used was a high-pressure mercury lamp, and the UV lamp intensity was set to 80 W / cm (cumulative light intensity 400 mJ / cm). 2 ). Furthermore, the aforementioned composition was coated onto a release PET substrate (Cosmo Peel E7006, manufactured by Toyobo Co., Ltd.) using a 4 mil applicator and cured under the same conditions as described above. Subsequently, a cured film was obtained by peeling off only the coating layer from the release PET substrate. This cured film was used to measure the storage modulus (Er) and loss tangent (tanδ) based on the method described above.

[0078] (Examples 2-12, Comparative Example 1) An active energy ray curable composition, a laminate produced using the same, and a cured film were obtained in the same manner as in Example 1, except that the raw materials were changed to the formulation (parts by mass) shown in Table 3.

[0079] [Table 3]

[0080] Details of Table 3 are shown below. Omnirad 1173 (IGM's "2-hydroxy-2-methyl-1-phenylpropan-1-one") Antifoaming agent (BYK054, manufactured by BYK Corporation) PGM-AC (Propylene glycol monomethyl ether acetate, manufactured by Toyo Petrochemical Co., Ltd.)

[0081] <Rating> The laminates obtained in the examples and comparative examples were evaluated for their print appearance and non-slip properties as described below. The evaluation results are shown in Table 3.

[0082] [Printed appearance] The coating layer of the laminates obtained in the examples and comparative examples was visually inspected, and the printed appearance was evaluated. The evaluation was performed according to the following criteria. A: The entire surface is uniform with no unevenness or air bubbles (very good) B: Slightly uneven, but no air bubbles (good) C: Some air bubbles are visible (usable) D: Numerous air bubbles are visible all over (unusable)

[0083] [Non-slip properties] Sample A, measuring 75 mm x 50 mm, was prepared by cutting out the printed portion of the laminate obtained in the examples and comparative examples in a constant temperature and humidity chamber maintained at 23°C and 50% humidity. Furthermore, Sample B, measuring 2 mm x 2 mm, was prepared by cutting out the printed portion of the same laminate. A 10 g weight, a cube measuring 2 mm x 2 mm x 2 mm, was attached to the substrate side of Sample B opposite to the coating layer. Next, sample A was fixed to a flat glass plate with the coating layer facing upwards, and sample B was gently placed on top of sample A so that its coating layer overlapped with the coating layer of sample A. Next, with one piece of glass plate fixed in place, the angle was gradually increased by raising the opposite side of the fixed edge. At this time, the angle at the moment when sample B, to which the weight was attached, slid down was recorded and evaluated according to the following criteria. A: 40 degrees or higher (very good) B: 30 degrees or higher, less than 40 degrees (good) C: 20 degrees Celsius or higher, less than 30 degrees Celsius (usable). D: Below 20 degrees (Not usable)

[0084] According to the evaluation results, the active energy ray curable composition of the present invention exhibits good non-slip properties and excellent print appearance. In particular, in Examples 1 and 2, where the ratio of the total number of isocyanate groups in the polyisocyanate component to the total number of hydroxyl groups in the monofunctional ethylenically unsaturated monomer having hydroxyl groups in the molecule was in the range of 0.80 to 0.99 in urethane acrylate (B), the cured film had increased elasticity, improved the feeling of the cured film resisting fingertip movements, and exhibited superior non-slip properties compared to Examples 3 and 4, where the ratio was below 0.80. Furthermore, in Examples 1 and 2, where the weight-average molecular weight of polyester polyol (A) was in the range of 2000 to 3000, the weight-average molecular weight after curing increased compared to Example 5, where the same value was below 2000, resulting in increased elasticity, improved sensation of the cured film resisting fingertip movement, and superior non-slip properties. Also, in Examples 1 and 2, where the glass transition temperature (Tg) of polyester polyol (A) was in the range of 90 to 115°C, the elasticity of polyester polyol (A) was moderately expressed compared to Examples 6 and 7, where the same value was below 90°C, resulting in improved sensation of the cured film resisting fingertip movement and superior non-slip properties. In addition, in Example 8, where the same value was above 115°C, the viscosity of the cured film was appropriately imparted, improving the sensation of it adhering to the fingertips and resulting in superior non-slip properties. Furthermore, the viscosity of the composition was reduced, resulting in excellent print appearance. Furthermore, in Examples 1 and 2, where the urethane acrylate (B) content in the total mass of the composition was in the range of 45-60%, the elasticity of the cured film increased with the increase in the urethane bond concentration in the composition, resulting in a better sense of resistance to fingertip movement and superior non-slip properties compared to Example 9, where the same value was less than 45%. In Examples 10 and 11, where the same value exceeded 60%, the viscosity of the composition was reduced, improving leveling during coating and resulting in superior printed appearance. In addition, the smoothness and defoaming properties of the printed surface increased, resulting in superior non-slip properties. Furthermore, the same effect as described above can be observed even when the printed layer is located between the substrate layer and the coating layer.

Claims

1. An active energy ray curable composition containing a polyester polyol (A) and a urethane acrylate (B), An active energy ray curable composition wherein the urethane acrylate (B) comprises a reaction product of a monofunctional ethylenically unsaturated monomer having a hydroxyl group in its molecule and polymeric diphenylmethane diisocyanate.

2. The active energy ray curable composition according to claim 1, wherein it does not contain an organic solvent, or the content of an organic solvent is 5% by mass or less of the total mass of the active energy ray curable composition.

3. An active energy ray curable composition according to claim 1 or 2, comprising a photopolymerization initiator.

4. The active energy ray curable composition according to claim 1 or 2, wherein the monofunctional ethylenically unsaturated monomer having a hydroxyl group in the molecule comprises a hydroxyalkyl (meth)acrylate.

5. The active energy ray curable composition according to claim 1 or 2, wherein the ratio (NCO / OH) of the total number of isocyanate groups in the polymeric diphenylmethane diisocyanate to the total number of hydroxyl groups in the monofunctional ethylenically unsaturated monomer having a hydroxyl group in the molecule is 0.50 to 1.

00.

6. The active energy ray curable composition according to claim 1 or 2, wherein the content of the urethane acrylate (B) is 40 to 80% by mass of the total mass of the active energy ray curable composition.

7. The active energy ray curable composition according to claim 1 or 2, wherein the storage modulus (Er) of the cured film, obtained by curing with active energy rays, is 1,000 to 2,500 MPa at 25°C, and the loss tangent (tanδ) at 25°C is 0.30 or less.

8. A coating composition comprising the active energy ray curable composition according to claim 1 or 2.

9. Having a base layer and a coating layer, A laminate in which the coating layer is formed from the coating composition described in claim 8.

10. The laminate according to claim 9, further comprising a printed layer between the substrate layer and the coating layer.

11. A method for manufacturing a laminate having a base layer and a coating layer, A method for manufacturing a laminate, comprising the step of applying the coating composition according to claim 8 onto a substrate by screen printing.

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