Water-dispersible adhesive composition and method for producing same, highly adhesive polyester film and coated article

Abstract

To provide an easily adhesive polyester film having good characteristics.SOLUTION: A production method of a water-dispersible adhesive composition comprises: reacting 1 mole of an isocyanate compound having (m+n) isocyanate groups with n moles of a hydroxyl group-containing (meth)acrylate compound; reacting a reaction product obtained with m moles of an alkylene oxide adduct of (meth)acrylic acid and the like to obtain an oligomer of a formula (1); while adding water to the oligomer, stirring or emulsifying an interface of the oligomer and water gently to prepare a water-soluble oligomer composition; and adding thereto a water-soluble polyester resin: (R1O-CONH)m-R2-(NHCO-OR3)n (1) (in the formula, R1O- represents a dehydrogenation residue of a polyalkylene glycol compound and the like having a hydroxyl group at one end; R2 a deisocyanated residue of the isocyanate compound; -OR3 is a dehydrogenation residue of the hydroxyl group-containing (meth)acrylate compound; and m and n represent integers of 1 to 50).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable water-dispersible adhesive composition, a method for producing the same, and a highly adhesive polyester film and coated article formed using the same. [Background technology]

[0002] Stretched polyester films have excellent transparency, dimensional stability and toughness, and are therefore used in a wide range of fields, such as base films for photographs, base films for magnetic tapes, films for making electrophotographic overhead projectors, metallized films and various packaging materials. However, because the surface of stretched polyester film is highly oriented, it has poor surface activity and poor adhesion to various binders, metal deposition layers, and printing inks that are applied to the film. For this reason, an easy-adhesion coating (primer coat) is applied to the polyester film. The easy-adhesion coating agent must be water-based because it is applied in-line. In addition, the easy-adhesion coating agent must contain polyester resin to improve adhesion to the polyester film. Recently, a method of blending an aqueous polyester resin with an aqueous acrylic resin or an epoxy resin has been developed, and in particular, a blend with an aqueous acrylic resin has been proposed that satisfies the substrate (untreated PET) adhesion, leveling properties, dimensional stability (winding performance), water resistance, moist heat blocking resistance (unwinding performance), and UV hard coat adhesion (e.g., Patent Documents 1 to 5). However, these methods cannot harden the surface of the easy-adhesion layer, and are insufficient in moist heat blocking resistance and scratch resistance during processing. On the other hand, active energy ray curing, typified by ultraviolet (UV) curing, is good for hardening the substrate surface, but it causes large curing shrinkage and poor dimensional stability of the film. In addition, there are no hard water-soluble UV resins, and forced emulsions of UV resins not only have poor solution stability, but also poor compatibility with water-based polyesters, resulting in a coating film with poor transparency and leveling properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP2002-371231A [Patent Document 2] Special Publication No. 6-13691 [Patent Document 3] Patent Publication No. 2005-029736 [Patent Document 4] Patent Publication No. 2014-65887 [Patent Document 5] Re-table 2012 / 98967 Summary of the Invention [Problem to be solved by the invention]

[0004] The present application aims to provide an active energy ray-curable, water-dispersible adhesive composition having the above-mentioned properties, which contains a water-soluble urethane (meth)acrylate having a specific form and a water-based polyester resin, and a production method thereof, as well as a highly adhesive polyester film and a coated article. [Means for solving the problem]

[0005] This application includes the following inventions: (1) reacting 1 mole of an isocyanate compound having (m+n) isocyanate groups with n moles of a hydroxyl group-containing (meth)acrylate compound; Next, the resulting reaction product is reacted with an alkylene oxide (meth)acrylate adduct or a polyalkylene glycol compound having a hydroxyl group at one end in an amount of m moles, Obtaining a urethane (meth)acrylate oligomer represented by formula (1), adding water to the urethane (meth)acrylate oligomer while gently stirring or emulsifying the interface between the urethane (meth)acrylate oligomer and water to prepare a water-soluble urethane (meth)acrylate oligomer composition; A method for producing a water-dispersible adhesive composition, comprising adding a water-soluble polyester resin to the water-soluble urethane (meth)acrylate oligomer composition. (R 1 O-CONH) m -R 2 -(NHCO-OR 3 ) n (1) (In the formula, R 1 O- is a dehydrogenation residue of a polyalkylene glycol compound having a hydroxyl group at one end or a (meth)acrylic acid alkylene oxide adduct; R 2 represents a residue of a deisocyanated group of an isocyanate compound, -OR 3 represents a dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound, m and n represent an integer between 1 and 50, provided that m≦n. (2) The method for producing the mixture described above, wherein the stirring is carried out using a paddle blade at a rotation speed of 100 rpm to 300 rpm. (3) The method for producing the above-described liquid, further comprising adding water until the solid content becomes 50% by mass or less, and continuing gentle stirring for a predetermined period of time after the addition of water is completed. (4) The method for producing the above-described method, wherein after the addition of the water is completed, stirring is continued for 10 minutes or more at a rotation speed of 100 rpm to 300 rpm. (5) The above-described production method, wherein the isocyanate compound is a diisocyanate or a polyisocyanate of a diisocyanate monomer. (6) The method for producing the above-described polyalkylene glycol compound having a hydroxyl group at one end thereof is an alkoxy polyalkylene glycol. (7) The method for producing the (meth)acrylic acid alkylene oxide adduct described above, wherein the (meth)acrylic acid alkylene oxide adduct is an alkylene oxide adduct of (meth)acrylic acid or a mono(meth)acrylate of polyalkylene glycol. (8) The method for producing the above-described hydroxyl group-containing (meth)acrylate compound is a hydroxyalkyl (meth)acrylate, a polyol (meth)acrylate or an alkylene oxide-added polyol (meth)acrylate. (9) An active energy ray-curable water-dispersible adhesive composition obtained by the production method described above. (10) The active energy ray-curable water-dispersible adhesive composition described above, further comprising at least one of a crosslinking agent and a photopolymerization initiator. (11) A highly adhesive polyester film comprising a polyester film and a layered cured product of the above-described water-dispersible adhesive composition laminated on the polyester film. (12) The highly adhesive polyester film described above, further comprising a hard coat layer laminated on the layered cured product. (13) A coated article comprising a substrate and a cured product of the above-described active energy ray-curable water-dispersible adhesive composition disposed on the surface of the substrate. Effect of the Invention

[0006] According to the present invention, it is possible to provide an active energy ray-curable water-dispersible adhesive composition having the above-mentioned properties, which contains a water-soluble urethane (meth)acrylate having a specific form and an aqueous polyester resin, a production method thereof, a highly adhesive polyester film, and a coated article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In this specification, "(meth)acrylate" and "(meth)acrylic acid" respectively mean "at least one selected from the group consisting of acrylate and methacrylate" and "at least one selected from the group consisting of acrylic acid and methacrylic acid".

[0008] [Method for producing water-dispersible adhesive composition] In the method for producing the water-dispersible adhesive composition, (a) providing a water-soluble urethane (meth)acrylate oligomer composition; (b) adding a water-soluble polyester resin to the obtained water-soluble urethane (meth)acrylate oligomer composition.

[0009] (a: Preparation of Water-Soluble Urethane (Meth)acrylate Oligomer Composition) The urethane (meth)acrylate oligomer contained in the water-soluble urethane (meth)acrylate oligomer composition is represented by formula (1). (R 1 O-CONH) m -R 2 -(NHCO-OR 3 ) n (1) (In the formula, R 1 O- is a dehydrogenation residue of a polyalkylene glycol compound having a hydroxyl group at one end or a (meth)acrylic acid alkylene oxide adduct; R 2 represents a residue of a deisocyanated group of an isocyanate compound, R 3 O- is a dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound, m and n represent an integer between 1 and 50, provided that m≦n. This urethane (meth)acrylate oligomer is reacting 1 mole ratio of an isocyanate compound having (m+n) isocyanate groups with n mole ratios of a hydroxyl group-containing (meth)acrylate compound; Next, a (meth)acrylic acid alkylene oxide adduct or a polyalkylene glycol compound having a hydroxyl group at one end is reacted in an m molar ratio to obtain the polyalkylene glycol. Then, while adding water to the obtained urethane (meth)acrylate oligomer, the interface between the urethane (meth)acrylate oligomer and the water is gently stirred, whereby a water-soluble urethane (meth)acrylate oligomer composition can be produced.

[0010] The emulsion obtained by the above-mentioned method for producing a water-soluble urethane (meth)acrylate oligomer composition in the present application has an extremely small average particle size and is stable (no secondary aggregation occurs) for a long period of time, while the coating film obtained by the composition containing the emulsion can be a coating agent excellent in water resistance, solvent resistance, and scratch resistance. In other words, it has unique contradictory properties, that is, it is water-soluble before curing, but when it becomes a cured product, it has high water resistance and solvent resistance. Such a coating film has excellent hard coat properties and scratch resistance, and also has antistatic properties, so it can protect the surface of a substrate such as plastic, prevent dust absorption, and even impart antibacterial properties. In addition, such a coating film has excellent anti-fogging properties because it has a hydrophilic group, and can be used not only for plastics but also for anti-fogging glasses, mirrors, etc., and can have good dispersibility in water-based pigments. Furthermore, since the weight average molecular weight of the urethane (meth)acrylate oligomer itself is relatively small, it can also be used as a component of a water-soluble UV inkjet ink.

[0011] Examples of the isocyanate compound having (m+n) isocyanate groups include diisocyanates and polyisocyanates of diisocyanate monomers. Examples of diisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (o-, m- or p-)xylene diisocyanate, methylene bis(cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate, norbornane diisocyanate, etc. Examples of polyisocyanates of diisocyanate monomers include nurates of hexamethylene diisocyanate, nurates of isophorone diisocyanate, nurates of tolylene diisocyanate, and biuretized products of these diisocyanates. Among these, nurates of hexamethylene diisocyanate, nurates of isophorone diisocyanate, and nurates of tolylene diisocyanate, each of which has three or more isocyanate groups in one molecule, are more preferred. The isocyanate compound may have a urethane structure in which an alcohol compound is added to one or more isocyanate groups contained therein, or a urea structure in which an amine compound is added. When an alcohol compound and an amine compound are added to an isocyanate group, the number of functional groups per molecule of the isocyanate compound can be increased. Examples of alcohol compounds that can be added to an isocyanate group include ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Examples of amine compounds include diaminoethane, diaminopropane, and tetramethylenediamine. It is preferable to use these alcohol compounds and amine compounds with a small weight average molecular weight per functional group from the viewpoint of increasing the scratch resistance of the cured polymer.

[0012] Examples of the hydroxyl group-containing (meth)acrylate compound include hydroxyalkyl (meth)acrylates, polyol (meth)acrylates, and alkylene oxide-added polyol (meth)acrylates. Examples of the hydroxyalkyl (meth)acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyphenoxypropyl (meth)acrylate. Examples of the polyol (meth)acrylates include glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Examples of the alkylene oxide-added polyol (meth)acrylates include alkylene oxide-added trimethylolpropane di(meth)acrylate, alkylene oxide-added pentaerythritol tri(meth)acrylate, and alkylene oxide-added dipentaerythritol penta(meth)acrylate.

[0013] When reacting an isocyanate compound with a hydroxyl group-containing (meth)acrylate compound, in order to promote the reaction, it is preferable to stir the mixture in the presence of a metal catalyst such as dibutyltin dilaurate or an amine catalyst such as 1,8-diazabicyclo[5.4.0]undecene-7 at a temperature range of 50°C to 80°C, more preferably at a temperature range of 60°C to 70°C.

[0014] Subsequently, the reaction product obtained above is reacted with an alkylene oxide (meth)acrylate adduct or a polyalkylene glycol compound containing a hydroxyl group at one end. The (meth)acrylic acid alkylene oxide adduct is preferably an alkylene oxide adduct of (meth)acrylic acid or a mono(meth)acrylate of polyalkylene glycol. The alkylene oxide adduct of (meth)acrylic acid is obtained by adding an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, to (meth)acrylic acid. It can also be synthesized from a polyalkylene glycol, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. The weight-average molecular weight of the (meth)acrylic acid alkylene oxide adduct can be selected arbitrarily, but is preferably 900 or more, more preferably 900 to 2000. From another viewpoint, the number of moles of the alkylene oxide added is preferably 20 or more, more preferably 20 to 35. The polyalkylene glycol compound containing a hydroxyl group at one end is preferably an alkoxypolyethylene glycol. Examples of the alkoxypolyethylene glycol include methoxypolyethylene glycol, ethoxypolyethylene glycol, butoxypolyethylene glycol, polyethylene glycol monoallyl ether, polyethylene glycol monododecyl ether, polyethylene glycol monolaurate, and polyethylene glycol monooctyl ether. The weight-average molecular weight of the alkoxypolyethylene glycol can be selected arbitrarily, but is preferably 900 or more, and more preferably 900 to 2000. By using such a compound, the water-soluble urethane (meth)acrylate oligomer composition obtained can be a nonionic emulsion, and even when various additives are added to a composition containing this, the inhibition of the properties of the emulsion, such as aggregation, precipitation, and separation, can be prevented.

[0015] When the reaction product obtained above is reacted with an alkylene oxide (meth)acrylate adduct or a polyalkylene glycol compound having a hydroxyl group at one end, the reaction is preferably carried out in the presence of a metal catalyst such as dibutyltin dilaurate at a temperature range of 50°C to 80°C, more preferably at a temperature range of 60°C to 70°C. The resin concentration of the obtained urethane (meth)acrylate oligomer can be 100%. The weight average molecular weight of the urethane (meth)acrylate oligomer can be, for example, 5000 to 100000, preferably 7000 to 20000. By using such a weight average molecular weight, a composition with an appropriate viscosity can be obtained, self-emulsification is easily caused, and the water-soluble composition can be easily adjusted using this, and when a coating film containing such a water-soluble composition is formed, a coating film with high hardness can be obtained. The weight-average molecular weight means the weight-average molecular weight calculated based on the molecular weight of standard polystyrene. The weight-average molecular weight was measured by a high-performance liquid chromatography (Shodex GPC system-11 type, manufactured by Showa Denko K.K.) using a column: Shodex GPC KF-806L (exclusion limit molecular weight: 2×10 7 , Separation range: 100~2×10 7 The measurement can be performed by using three columns in series (theoretical plate number: 10,000 plates / column, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm).

[0016] For example, when an isocyanate compound having (m+n) isocyanate groups is reacted with an alkylene oxide (meth)acrylate adduct or a polyalkylene glycol compound having a hydroxyl group at one end first, the polyalkylene glycol compound has a distribution in weight average molecular weight, and polyalkylene glycols having not only a hydroxyl group at one end but also hydroxyl groups at both ends are present, so gelation often occurs. When gelation occurs, not only is the reaction unable to proceed stably, but the resulting reaction product is also difficult to dissolve in water. On the other hand, as described above, by first reacting an isocyanate compound having (m+n) isocyanate groups with n molar ratio of a hydroxyl group-containing (meth)acrylate compound and then reacting it with a (meth)acrylic acid alkylene oxide adduct compound or a polyalkylene glycol compound containing a hydroxyl group at one end, the polyalkylene glycol compound is bonded in a pendant-like manner to form a pendant-type urethane acrylate structure, which enables self-emulsification.

[0017] Next, water is added to the urethane (meth)acrylate oligomer represented by formula (1) to produce a water-soluble urethane (meth)acrylate oligomer composition in the form of an emulsion liquid. For this purpose, water is gradually added to the urethane (meth)acrylate oligomer obtained above. At this time, the obtained urethane (meth)acrylate oligomer is preferably maintained at a temperature in the range of, for example, 30°C to 80°C, and the temperature of the water to be added is also preferably adjusted to the same range, more preferably to a temperature range of 40°C to 70°C or 40°C to 60°C. The water to be added may be tap water, deionized water, ion-exchanged water, distilled water, or other water. The water is preferably added by, for example, dropping or divided. In the case of divided addition, the amount of water added at one time is, for example, 50% by mass to 200% by mass, preferably 100% by mass to 200% by mass of the urethane (meth)acrylate oligomer. The amount of water added is preferably an amount that results in a resin content concentration of 50% by mass or less, more preferably 10% by mass to 45% by mass, and even more preferably 15% by mass to 40% by mass or 20% by mass to 40% by mass. For example, the time required for adding water may be 5 minutes or more from the start to the end of the addition of water, and is preferably 5 minutes to 2 hours, and more preferably 10 minutes to 30 minutes or 15 minutes to 30 minutes.

[0018] Also, at the same time as the addition of water, it is preferable to place a stirring blade near the interface between the oligomer and water, that is, near the interface between the oligomer and water, or slightly on the water side of the interface, and stir. Here, it is preferable to stir gently. In addition, when stirring with a stirrer, the stirring bar sinks to the bottom of the container and cannot be placed at the interface between the oligomer and water, that is, the W / O interface, so it is preferable to stir using a stirrer that can place a stirring blade near the interface between the oligomer and water. As the stirring blade, for example, a paddle blade can be used. The paddle blade can be placed near the interface between the oligomer and water, or slightly on the water side of the interface, and may have only one blade, or may have two or more blades in multiple stages. For gentle stirring, a rotation speed of 500 rpm or less can be mentioned, preferably 300 rpm or less, more preferably 200 rpm or less, and particularly preferably 100 rpm to 300 rpm or 100 rpm to 150 rpm. Furthermore, it is preferable to continue stirring even after the addition of water is completed. The stirring in this case may be different from the stirring during the addition, but it is preferable to continue stirring at the same rate. After the addition of water is completed, stirring may be continued for, for example, 10 minutes or more, preferably 20 minutes or more, and more preferably 30 minutes or more. The rotation speed in this case may be in the same range as above.

[0019] By emulsifying by such an emulsification method (phase inversion emulsification), the obtained emulsion has an extremely small average particle size and high storage stability. In addition, when the emulsion is used as an adhesive composition, for example, coated and dried, and then cured with active energy rays, the obtained coating film has good leveling properties and extremely high water resistance, and an adhesive composition having contradictory properties can be obtained in which the oligomer before curing is water-soluble, while the coating film after curing has high water resistance. It has been confirmed that this is due to the fact that the particle size of the urethane (meth)acrylate oligomer in the obtained water-soluble urethane (meth)acrylate oligomer composition is made into uniform fine particles. For example, in the particle size distribution of the emulsion particles, the particle size of 50% of the particles is 100 nm or less. In addition, the 50% particle size is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 10 nm to 45 nm. In addition, the 95% cumulative particle size is 150 nm or less. Also, 95% of the particle size is preferably 140 nm or less, more preferably 120 nm or less, and even more preferably 30 nm to 115 nm. From another viewpoint, the arithmetic mean diameter may be 110 nm or less. Also, it is preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 10 nm to 60 nm. These values ​​were obtained by measuring the particle size distribution of the emulsion using a dynamic light scattering particle size distribution measuring device (LB-500) manufactured by Horiba, Ltd.

[0020] In the present application, an emulsion of a urethane (meth)acrylate oligomer composition obtained by subjecting a specific hydroxyalkyl acrylate to an n-functional isocyanate group at (1 to n-1) / n mol % addition reaction, and then subjecting a polyalkylene glycol compound containing a hydroxyl group at one end or a (meth)acrylic acid alkylene oxide compound containing a hydroxyl group at one end to an addition reaction at (1 to n-1) / n mol % addition reaction with the n-functional isocyanate group is preferred. When such an emulsion is used as a radiation-cured coating film, it can have both excellent hard coat properties and durability (water resistance and solvent resistance). For example, when a polyalkylene glycol compound containing a hydroxyl group at one end that does not have a polymerizable functional group is used during the synthesis of a urethane (meth)acrylate oligomer, if the ratio of this compound is increased, the curing property decreases when crosslinked and the hardness also tends to decrease. Therefore, it is preferable to set the molar ratio of the polyalkylene glycol compound containing a hydroxyl group at one end to the molar ratio of the (meth)acrylate compound containing a hydroxyl group or less. The larger the weight average molecular weight of the polyalkylene glycol chain, the greater the antistatic effect when crosslinked, but the lower the hardness tends to be. In addition, the greater the number of functional groups in the (meth)acrylate compound containing a hydroxyl group, the greater the hardness when crosslinked, and conversely, the fewer the number, the lower the hardness. By adjusting these, a cured polymer with an appropriate hardness can be obtained.

[0021] (b: Addition of water-based polyester resin) Next, an aqueous polyester resin is added to the water-soluble urethane (meth)acrylate oligomer composition obtained above. The aqueous polyester resin preferably contains, for example, a sulfonate and / or a carboxylate in the molecule, and more preferably contains a polyester resin having a weight average molecular weight of 2,500 to 30,000. The polyester resin is preferably a polyester resin having a weight average molecular weight of 2,500 to 30,000 and a carboxyl group concentration of 140 KOHmg / g or less, in which the polycarboxylic acid component is composed of an aromatic dicarboxylic acid not containing a metal sulfonate salt group, an aliphatic or alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid containing a metal sulfonate salt group, and the polyol component is composed of an aliphatic glycol and / or an alicyclic glycol having 6 to 12 carbon atoms (see, for example, the description in JP-B-6-13691). Examples of aromatic dicarboxylic acids not containing a metal sulfonate salt group include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. Examples of aliphatic or alicyclic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Examples of aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, and neopentyl glycol. Examples of alicyclic glycols having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol. Examples of the dicarboxylic acid containing a metal sulfonate group include metal salts of sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, etc. Examples of the metal salts include salts of Li, Na, K, Mg, Ca, Cu, Fe, etc. The polyester resin may be used alone or in combination of two or more kinds. Such polyester resins may be produced by known methods.

[0022] The polyester resin may be added directly to the water-soluble urethane (meth)acrylate oligomer composition, but is preferably added as an aqueous polyester resin composition obtained by dissolving the polyester resin in a solvent. The solvent preferably contains at least one selected from water and water-soluble organic solvents. The water-soluble organic solvent is an organic solvent having a solubility of 20 g or more per 1 g of water at 20°C. Examples of the water-soluble organic solvent include aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds. Examples of the water-soluble organic compounds include monohydric alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and tert-butanol, glycols such as ethylene glycol and propylene glycol, glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, tert-butyl cellosolve, 3-methyl-3-methoxybutanol, and n-butyl cellosolve acetate, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone, cyclohexanone, cyclooctanone, cyclodecanone, and isophorone. These water-soluble organic compounds may be used alone or in combination. Among them, n-butyl cellosolve, tert-butyl cellosolve, ethyl cellosolve, isopropanol, and the like, and aqueous solutions thereof are preferred. The boiling point of these water-soluble organic solvents is more preferably in the range of 60 to 200°C. The aqueous polyester resin may contain an acrylic acid ester copolymer resin. For example, it may contain a structural unit derived from an acrylic acid ester and / or a methacrylic acid ester, an acrylic acid salt and / or a methacrylic acid salt, or the like, and may be a copolymer resin having a Tg of 5°C to 105°C, preferably 30°C to 110°C, and more preferably 50°C to 80°C. Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, and examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. Examples of the acrylic acid salt and the methacrylic acid salt include metal salts such as Li, Na, and K, and organic salts such as ammonia, monoethanolamine, and diethanolamine. When such a resin is contained, blocking resistance can be improved.

[0023] Specific examples of the aqueous polyester resin composition include: GOO Chemical Industry Co., Ltd. PLASCOAT Z-221, Z-446, Z-561, Z-687 (sulfonate, solvent: water), Z-565, Z-592, Z-690, Z-880, Z-3310, RZ-105, RZ-570 (sulfonate, solvent: water, t-butyl cellosolve), Z-730 (carboxylate, solvent: water), Z-760 (carboxylate, solvent: water, t-butyl cellosolve), Takamatsu Oil Co., Ltd. PES Resin A series, A-110, A-160P, A-520, A-613D, A-615GE, A-640 (sulfonate, solvent: water), A-120, A-124GP, A-125S (sulfonate, solvent: water, butyl cellosolve), A-680, A-684G, A-690, A-695GE (carboxylate, solvent: water), Elitel (registered trademark) KT-0507, KT-8904, KT-8701, KT-9204, KT-8803 (solvent: water), KA-0134, KA-5034, KA-6137, KA-3556 (solvent: water, isopropanol) manufactured by Unitika Ltd. Vylonal (registered trademark) MD-1480, MD-2000 (solvent: water), MD-1200, MD-1500, MD-1985 (solvent: water, butyl cellosolve) manufactured by Toyobo Co., Ltd. Mitsubishi Chemical Corporation's Nichigo Polyester (registered trademark) WR-901, WR-905 (sulfonate, solvent: water), WR-961, W-1031 (carboxylate, solvent: water), HR-521, HR-531 (carboxylate, solvent: water, butyl cellosolve), Aronmelt (registered trademark) PES2353A25, PES2000W30, PES2005A30 manufactured by Toagosei Co., Ltd. Examples of composite resins made of polyester-(meth)acrylic acid ester copolymer include the PES resin A series manufactured by Takamatsu Oil Co., Ltd., A-645GH and A-647GEX (sulfonate, solvent: water). The water-soluble polyester resin to be added to the water-soluble urethane (meth)acrylate oligomer composition is preferably a sulfonate type rather than a carboxylate type, since this has better leveling properties during coating. Furthermore, the water-soluble polyester resin is preferably a mixed resin of a polyester resin and / or a (meth)acrylic acid ester copolymer resin having a Tg (glass transition point) of 5° C. to 105° C., preferably 30° C. to 80° C., from the viewpoint of improving heat blocking resistance. The water-soluble polyester resin can be added to the water-soluble urethane (meth)acrylate oligomer composition by adding the polyester resin dissolved in water or the water-soluble organic solvent as described above and stirring. The ratio of the water-soluble urethane (meth)acrylate oligomer composition and the water-soluble polyester resin is preferably, for example, 40% by mass to 60% by mass / 60% by mass to 40% by mass.

[0024] [Active Energy Ray-Curable Water-Dispersible Adhesive Composition] The water-dispersible adhesive composition obtained by the above-mentioned production method can be cured by irradiation with active energy rays. Examples of active energy rays include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X-rays, gamma rays, etc. The irradiation dose is not particularly limited, and is, for example, 100 mJ / cm. 2 to 2000mJ / cm 2 and 500 mJ / cm 2 to 1000mJ / cm 2 The range is preferably: The water-dispersible adhesive composition of the present application obtained as described above may further contain a crosslinking agent, a photopolymerization initiator and a photopolymerization initiation aid, an ethylenically unsaturated monomer, an antistatic agent, and the like.

[0025] (Crosslinking agent) By incorporating a crosslinking agent into the water-dispersible adhesive composition of the present application, the adhesiveness of the coating film formed by the composition under high temperature and high humidity conditions can be further improved. Furthermore, the introduction of a crosslinked structure into the coating film improves the solvent resistance, and therefore the appearance of interference fringes due to variations in coating thickness can be more suitably suppressed. Examples of the crosslinking agent include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based, and carbodiimide-based agents. Specifically, any of the known agents used in the field, such as those described in JP-A-2014-65887, may be used. Among these, melamine-based and oxazoline-based agents are preferred in terms of the stability over time of the coating liquid and the effect of improving adhesion under high temperature and high humidity treatment. In addition, a catalyst or the like is appropriately used as necessary to promote the crosslinking reaction. The content of the crosslinking agent is preferably from 5% by mass to 50% by mass, and more preferably from 10% by mass to 30% by mass, of the solid content from the viewpoints of the strength of the coating film, adhesion under high temperature and high humidity conditions, flexibility of the coating film, etc. The solid content here is also called the resin concentration or heating residue, and means the value measured by the method for measuring the heating residue described in the Examples. From another point of view, the water-soluble urethane (meth)acrylate oligomer composition / (water-soluble polyester resin+crosslinking agent) is preferably in the range of 100 parts by mass / (50 parts by mass to 150 parts by mass) in terms of solid content ratio, and more preferably 100 parts by mass / (70 parts by mass to 130 parts by mass). department / 30 parts by mass ~ 90 parts by mass / 10 parts by mass department The range of 80 mass department / 20 parts by mass ~ 85 parts by mass / 15 parts by mass department is more preferred. Among them, when the crosslinking agent is to be blended with the aqueous polyester resin, the aqueous melamine-based Watersol S-695 (manufactured by DIC Corporation, aqueous melamine, 60% solids) and the aqueous oxazoline-based Epocross WS700 (manufactured by Nippon Shokubai, acrylic containing oxazoline groups, 25% solids) are preferred. In this case, the ratio of aqueous polyester resin to crosslinking agent is 70 by mass. department ~90 mass department / 10 mass department ~30 mass department (solid content ratio), particularly 75 mass department ~85 mass department / 15 mass department ~25 mass department It is preferable to add it within the range of (solid content ratio).

[0026] (Photopolymerization initiator) By adding a photopolymerization initiator to the water-dispersible adhesive composition, the urethane (meth)acrylate oligomer can be crosslinked and / or polymerized more easily to form a cured polymer by irradiation with active energy rays, such as ultraviolet rays. This cured polymer exhibits excellent scratch resistance, surface hardness, and adhesion to plastic substrates. The photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light, and examples thereof include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylenephenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl Ketals, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4',4"-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenyl glyoxylate, benzil, 9,10-phenanthrenequinone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and the like. In particular, in order to make the water-soluble urethane (meth)acrylate oligomer composition function better, it is preferable to use a photopolymerization initiator that is water-soluble or water-dispersible. Examples of such photopolymerization initiators include 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthone-9-one methchloride (manufactured by Octel Chemicals, "Quantacure QTX"), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals, "Irgacure 2959"), etc., and among them, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals, "Irgacure 2959") is more preferable. The photopolymerization initiator can be used in an amount of 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 2 to 8 parts by mass, and particularly preferably 3 to 5 parts by mass, relative to 100 parts by mass of the solid content of the water-soluble urethane (meth)acrylate oligomer emulsion.

[0027] (Photopolymerization initiator aid) A photopolymerization initiator assistant may be used together with the photopolymerization initiator. Examples of the photopolymerization initiator assistant include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid (n-butoxy)ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. The photopolymerization initiation aid may be used in an amount of 0.1 to 100 parts by mass relative to 100 parts by mass of the photopolymerization initiator.

[0028] (ethylenically unsaturated monomer) Examples of the ethylenically unsaturated monomer to be added to the urethane (meth)acrylate oligomer include a (meth)acrylic acid compound and a vinyl group-containing compound. Examples of (meth)acrylic acid compounds include acrylic acid amides, alkyl (meth)acrylates, aminoalkyl (meth)acrylates, quaternary salts of aminoalkyl (meth)acrylates, alkoxy polyalkylene glycol (meth)acrylates, hydroxyalkyl (meth)acrylates, acid anhydride adducts of hydroxyalkyl (meth)acrylates, polyalkylene glycol di(meth)acrylates, alkyl diol di(meth)acrylates, polyol poly(meth)acrylates, and alkylene oxide-added polyol poly(meth)acrylates. Examples of vinyl group-containing compounds include vinyl acetate, N-vinyl acetamide, vinyl pyrrolidone, vinyl alkyl ethers, vinyl sulfonic acid, and salts of vinyl sulfonic acid. These may be used alone or in combination of two or more.

[0029] Examples of acrylic acid amides include (meth)acryloyl morpholine and dimethylamino alkyl (meth)acrylamide. Examples of amino alkyl (meth)acrylates include diethylamino ethyl (meth)acrylate. Examples of quaternary salts of amino alkyl (meth)acrylates include alkyloyl amino propyl dimethyl-2-hydroxyethyl ammonium salt. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, etc. Examples of alkoxy polyalkylene glycol (meth)acrylates include methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, etc. Examples of hydroxy alkyl (meth)acrylates include hydroxy ethyl (meth)acrylate, hydroxy propyl (meth)acrylate, etc. Examples of the acid anhydride adduct of hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate phthalic anhydride adduct, hydroxyethyl (meth)acrylate succinic anhydride adduct, hydroxyethyl (meth)acrylate tetrahydrophthalic anhydride adduct, hydroxyethyl (meth)acrylate hexahydrophthalic anhydride adduct, hydroxypropyl (meth)acrylate phthalic anhydride adduct, hydroxypropyl (meth)acrylate succinic anhydride adduct, hydroxypropyl (meth)acrylate tetrahydrophthalic anhydride adduct, and hydroxypropyl (meth)acrylate hexahydrophthalic anhydride adduct. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate. Examples of alkyl diol di(meth)acrylates include butane diol di(meth)acrylate and hexane diol di(meth)acrylate.Examples of polyol poly(meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of alkylene oxide-added polyol poly(meth)acrylates include alkylene oxide-added trimethylolpropane tri(meth)acrylate, alkylene oxide-added pentaerythritol tri(meth)acrylate, alkylene oxide-added pentaerythritol tetra(meth)acrylate, and alkylene oxide-added pentaerythritol hexa(meth)acrylate. Examples of vinyl alkyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, amyl vinyl ether, and 2-ethylhexyl vinyl ether.

[0030] Among these, the (meth)acrylic acid compound or the vinyl group-containing compound is more preferably (meth)acryloylmorpholine, vinylpyrrolidone, dimethylaminoalkyl (meth)acrylate, a quaternary salt of dimethylaminoalkyl (meth)acrylate, dimethylaminoalkyl (meth)acrylamide, N-vinylacetamide, vinylsulfonic acid, or a vinylsulfonate salt, which have antistatic properties. The ethylenically unsaturated monomer is used in an amount of 0 to 100 parts by mass, preferably 0.02 to 80 parts by mass, per 100 parts by mass of the water-soluble urethane (meth)acrylate oligomer composition (resin concentration: 20% by mass).

[0031] (Antistatic agent) An antistatic agent may be added to the water-soluble urethane (meth)acrylate oligomer composition. This acts synergistically with the antistatic effect of the cured polymer when crosslinked, and the antistatic effect is significantly improved. By setting the amount of the antistatic agent within the following range, for example, the antistatic agent is not lost from the cured polymer when crosslinked, and a sufficient antistatic effect can be obtained. Examples of the antistatic agent include cationic antistatic agents of quaternary ammonium salts, at least one anionic antistatic agent selected from aliphatic sulfonates, higher alcohol sulfates, higher alcohol alkylene oxide adduct sulfates, higher alcohol phosphates, and higher alcohol alkylene oxide adduct phosphates, and at least one nonionic antistatic agent selected from higher alcohol alkylene oxide adducts and polyalkylene glycol fatty acid esters. Of these, cationic antistatic agents are preferred. The antistatic agent can be used in an amount of 0 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the water-soluble urethane (meth)acrylate oligomer composition (resin concentration: 20% by mass).

[0032] The water-dispersible adhesive composition may further contain fillers, dyes and pigments, oils, plasticizers, waxes, drying agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, defoamers, leveling agents, thixotropy-imparting agents, antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, crosslinking agents, etc. Any of the above-mentioned agents commonly used in the art may be used. If necessary, the solvent may contain an organic solvent such as ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves, and diacetone alcohol.

[0033] The water-dispersible adhesive composition can be used in a variety of applications by forming a cured product thereof onto a variety of substrates. Examples of substrates include plastics (e.g., polyolefin resins such as polyethylene, particularly polyethylene terephthalate, polypropylene, polycyclopentadiene, etc., polycarbonate, polyester, ABS resin, acrylic resin, etc.), glass, paper, wood, cement, etc. In particular, when a coating film of the water-dispersible adhesive composition is laminated as a layered cured product on a polyethylene film, it can be used as an easily adhesive polyester film. By forming the water-dispersible adhesive composition on a substrate in this manner, it is possible to adhere the composition to an untreated substrate without the need for a primer treatment, etc. The cured product of such a coating film has excellent scratch resistance and antistatic properties in addition to adhesiveness. When the water-dispersible adhesive composition is formed on the surface of the substrate, the thickness is, for example, 0.01 μm to 100 μm, preferably 0.5 μm to 10 μm. In addition, before irradiating with active energy rays, it is preferable to perform hot air drying and heat treatment at a temperature exceeding 100° C., 110° C. or more, 120° C. or more, and 150° C. or less for 1 to 10 minutes, or 5 to 10 minutes. This prevents moisture from remaining in the coating film, prevents the coating film from whitening in appearance, and improves adhesion to the substrate. In addition, the leveling of the surface of the cured product by the coating film is improved, and the steel wool resistance can be improved. In particular, it can be applied with better adhesion as a polyester film that is easily adhesive to untreated PET. In particular, when a crosslinking agent is contained in the water-dispersible adhesive composition, crosslinking under high-temperature heat treatment improves adhesion to the substrate and solvent resistance to the hard coat coating solution solvent. The coated article thus obtained can protect the surface of a substrate such as plastic and prevent dust absorption. In addition, it has excellent anti-fogging properties and can be used to prevent fogging not only of plastics but also of glasses, mirrors, etc. In particular, the transparent biaxially oriented, highly adhesive polyester film can be used mainly as a touch panel film for personal computers and mobile devices, car navigation systems, etc., displays such as computers, televisions, and liquid crystal display devices, kitchen cabinets, decorative materials around vanity washstands, etc. Furthermore, various functional layers, for example, a hard coat layer, may be further formed on the substrate having the cured product laminated on the surface thereof. In this case, the cured product of the water-dispersible adhesive composition can improve the adhesion between the substrate and the functional layer. EXAMPLES

[0034] Examples of the present invention will be described in detail below. Water-soluble urethane (meth)acrylate oligomer compositions of the present invention were produced as follows. Synthesis Example 1: Water-soluble urethane (meth)acrylate oligomer composition (Production of Urethane (Meth)acrylate Oligomer Composition) In a four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a dry air inlet, 159 g (0.29 mol) of hexamethylene diisocyanate trimer (isocyanate group content 23%), 0.6 g of 2,6-di-tert-butylcresol, and 0.02 g of dibutyltin dilaurate were charged. Dipentaerythritol pentaacrylate (0.58 mol) (545 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 59.8 mgKOH / g)) was added dropwise to the flask at 70°C over about 1 hour, and the mixture was allowed to react at 70°C for 4 hours. The mixture was cooled to 60°C when the remaining isocyanate group reached 1.7%. Further, 643.9 g (0.30 mol) of polyethylene glycol monomethyl ether (weight average molecular weight 989.59, hydroxyl value 56.7 mgKOH / g) was added dropwise at 55° C. over about 1 hour. When the reaction started, heat was generated intensely, so the mixture was cooled as needed. When the heat generation had almost subsided, the mixture was heated to 70° C. and reacted for 3 hours. The infrared absorption spectrum of the oligomer was measured, and the absorption spectrum of the isocyanate group (2280 cm -1 The reaction was terminated when the disappearance of the urethane acrylate oligomer (resin concentration: 100%) was obtained. The weight average molecular weight of the obtained urethane acrylate oligomer was 12,000. (emulsification) 300g of the urethane acrylate oligomer obtained above was kept at 60°C, and 700g of ion-exchanged water at room temperature (25°C) was added dropwise or divided into five times (initial 400g, 100g added every 30 minutes) (phase inversion emulsification method) while stirring with a paddle blade near the interface between the oligomer and the ion-exchanged water (W / O interface). The stirring was performed at 100 to 150 rpm. The dropwise addition was stopped when the resin concentration reached 30%, and an emulsion was obtained. Stirring was then continued for 30 minutes to obtain a water-soluble urethane (meth)acrylate oligomer composition [A-1]. The resulting water-soluble urethane (meth)acrylate oligomer composition had a pH of 4 to 5, a heating residue (hereinafter also referred to as "resin concentration") of 30% by weight, and a viscosity at 25°C of 10 mPa·S.

[0035] Synthesis Example 2: Water-soluble urethane (meth)acrylate oligomer composition (Production of Urethane (Meth)acrylate Oligomer Composition) Instead of the dipentaerythritol pentaacrylate (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) in Synthesis Example 1, pentaerythritol triacrylate (0.58 mol) (260 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value 125.4 mgKOH / g) was added dropwise over about 1 hour, and the reaction was carried out at 70° C. for 4 hours. When the residual isocyanate group reached 2.9%, the mixture was cooled to 60° C. Further, 296 g (0.30 mol) of polyethylene glycol monomethyl ether (weight average molecular weight 989.59, hydroxyl value 56.7 mgKOH / g) was added dropwise at 55° C. over about 1 hour. When the reaction started, intense heat was generated, so the mixture was cooled as needed. When the heat generation had almost subsided, the mixture was heated to 70° C. and reacted for 3 hours. The infrared absorption spectrum of the oligomer was measured, and the absorption spectrum of the isocyanate group (2280 cm -1 The reaction was terminated when the disappearance of the urethane acrylate oligomer (resin concentration: 100%) was obtained. The weight average molecular weight of the obtained urethane acrylate oligomer was 6,000. (emulsification) 300g of the urethane acrylate oligomer obtained above was kept at 60°C, and 700g of ion-exchanged water at room temperature (25°C) was added dropwise or divided into five times (initial 400g, 100g added every 30 minutes) (phase inversion emulsification method) while stirring with a paddle blade near the interface between the oligomer and the ion-exchanged water (W / O interface). The stirring was performed at 100 to 150 rpm. The dropwise addition was stopped when the resin concentration reached 30%, and an emulsion was obtained. Stirring was then maintained for 30 minutes, and a water-soluble urethane (meth)acrylate oligomer composition [A-2] was obtained. The resulting water-soluble urethane (meth)acrylate oligomer composition had a pH of 4 to 5, a heating residue of 30% by weight, and a viscosity of 35 mPa·S at 25°C. The heating residue and viscosity are values ​​measured by the following methods.

[0036] (heated residue) Accurately measure the weight of an aluminum dish (approximately 50 mm in diameter) (Ag), place approximately 1.5 g of the sample on the dish, quickly spread it as evenly as possible over the entire bottom surface with a glass rod, and then accurately measure its mass (Bg). Dry the aluminum dish in an electric constant temperature dryer at 105°C to 110°C for 3 hours. Remove the aluminum dish from the dryer, allow it to cool to room temperature, and then accurately measure its weight (Cg). Heating residue (mass%)=100×{(CA) / (BA)} Here, A is the mass of the aluminum plate (g), B is the mass of the aluminum plate including the sample before drying (g), and C is the mass of the aluminum plate including the sample after drying (g). (viscosity) Place approximately 400 ml of sample in a wide-mouth bottle, cover it, place it in a thermostatic bath adjusted to the temperature "specified in the quality standard," and leave it for at least four hours to adjust the temperature of the sample. Place a rotor "specified in the quality standard" that has been kept at a specified temperature of ±0.2°C in a B-type rotational viscometer into the sample while being careful not to allow air bubbles to adhere to it, attach the rotor to the viscometer, and align the liquid level with the marked line. Set the rotation speed "specified in the quality standard," rotate the viscometer, and read the pointer reading after one minute. Viscosity (mPa S) = Pointer reading x X Here, X is the viscosity conversion multiplier (according to the conversion table attached to the B-type rotational viscometer).

[0037] Example 1 In a four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and dry air inlet, 333 g of an emulsion of a water-soluble urethane (meth)acrylate oligomer composition [A-1] (solid content 30%) was added with (B-1) PLASCOAT RZ-105 (-SO3Na grade, acid value <5 mgKOH / g, water-based (t-butyl cellosolve 10%), Tg: 52°C, pencil hardness 2H, solid content 25%, RI = 1.56, manufactured by GOO Chemical Industry Co., Ltd.). A water-dispersible adhesive composition (solids content 20%) was obtained by heating and dissolving 320 g of (C-1) Watersol S-695 (DIC Corporation, water-based melamine, solids content 60%), 33 g of (C-2) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals Corporation, "Irgacure 2959") and 313 g of ion-exchanged water at 60°C. Examples 2 to 4 and Comparative Examples 1 to 5 The components shown in Table 1 below were mixed to prepare water-dispersible adhesive compositions of Examples and Comparative Examples in the same manner as in Example 1. The components in Table 1 are as shown in Table 2. [Table 1] [Table 2]

[0038] Test Example A Each of the water-dispersible adhesive compositions obtained in the Examples and Comparative Examples was applied to an untreated PET film (substrate A) using a bar coater #14 so that the film thickness after drying would be 1 μm to 2 μm. After coating the water-dispersible adhesive composition, the coating was dried and heat-treated at 120°C for 5 minutes, and then irradiated with an electrodeless lamp H bulb at a line speed of 5.4 m / min and a radiation dose of 600 mJ / cm. 2 , Peak illuminance: 1,500mW / cm 2Thereby, an easily adhesive polyester film was formed in which each water-dispersible adhesive composition was laminated as an easily adhesive layer. These highly adhesive polyester films were used to carry out the following evaluations. (Coating appearance and leveling) The coating appearance and leveling property of the easily adhesive polyester film were visually confirmed based on the presence or absence of whitening, unevenness (non-uniformity) and repelling of the coating film. A coating film that was transparent and had no repelling was a uniform and transparent coating film, and was evaluated as good (◯). In addition, the water-dispersible adhesive compositions of the Examples and Comparative Examples, which were rated as good for coating film appearance and leveling property, were laminated onto substrate A and substrate C to give highly adhesive polyester films with dry film thicknesses of 1 to 2 μm, and the following evaluations were carried out. (Dimensional stability: Suitable for winding) The obtained adhesive polyester film was cut into a 10 cm x 10 cm square and left overnight. The jump height was measured at four points on the edge and the average value was calculated. The values ​​are shown in Table 3 (unit: mm). When the cure shrinkage was 0 mm for the 125 μm thick substrate A, the same evaluation was performed for the 50 μm thick substrate C. When the cure shrinkage was 0 mm for the 50 μm thick substrate C, the winding suitability was judged to be good. The results are shown in Table 3. [Table 3]

[0039] Test Example B The following tests were carried out on the highly adhesive polyester film prepared in Test Example A. The results are shown in Table 4. (Adhesion to substrate) The adhesion of the easy-adhesion layer to the substrate was evaluated. According to JIS K5400, 100 2 mm and 1 mm squares were made on the cured coating film of each water-dispersible adhesive composition obtained in the Examples and Comparative Examples, and an adhesion test was performed using cellophane tape. The peeling state of the squares was observed, and the number of remaining squares was counted. Comparative Examples in which the adhesion to the substrate was less than 100 were rated as x, and the blocking resistance, abrasion resistance, optical properties, and the like were not evaluated. (Film unwinding) The adhesive surface of the polyester film was placed on top of the adhesive surface, cut into a 5 cm x 5 cm square, and the room temperature blocking property and the wet heat blocking property were evaluated using an ink blocking tester (manufactured by DG Engineering Co., Ltd.). Blocking property at room temperature: 23℃×32%RH×300g / cm 2 load ※ ×Easy peeling after 24 hours Moisture and heat blocking resistance: 50℃×80%RH×300g / cm 2 load ※ ×Easy peeling after 24 hours ※ :300g / cm 2 Load: 300 x 5cm x 5cm = 7.5kg (Blocking tester spring scale: 22.3mm) In terms of blocking properties, those that peeled lightly and easily were rated ◯, those that peeled by zipping were rated ◯△ (all were passed), those that could not be peeled easily were rated ×, and those that were bonded and could not be peeled at all were XX (both were failed). (Abrasion resistance) The adhesive layer of the polyester film was rubbed 10 times with steel wool (#0000) under a load of 50 g to evaluate the scratch resistance. The state of scratches was visually observed. (Coating Hardness) The pencil hardness of the adhesive layer of the adhesive polyester film was measured in accordance with JIS K5400. (Flexibility: Mandrel test) To evaluate the flexibility of the adhesive layer of the adhesive polyester film, a mandrel tester was used in accordance with JIS K5600 to measure the mandrel diameter φ (mm) at which a crack first occurred. If no cracks occurred even at the minimum mandrel diameter of 2φ (mm), the film was bent 180° once (described as 1T). At 1T, if white streaks appear on the film, write "2φ(mm) OK, 1T ×". (Optical properties) The total light transmittance of the highly adhesive polyester film was measured using a spectrophotometer CM-3600A manufactured by Konica Minolta. A total light transmittance of 89% or more was considered to be acceptable (substrate A: 88.4% or more). [Table 4]

[0040] Test example C: UV topcoat adhesion A water-based, solventless and solvent-based UV topcoat was applied to the adhesive layer of the adhesive polyester film prepared in Test Example A using a bar coater No. 16 so that the film thickness after drying would be 2 μm to 5 μm. The water-based and solvent-based topcoats were dried at 80° C. for 3 minutes after application. Then, the electrodeless lamp H bulb (line speed: 5.4 m / min, irradiation amount: 600 mJ / cm 2 , Peak illuminance: 1, 500mW / cm 2 ) to form a coating film as a hard coat laminate. In accordance with JIS K 5400, 100 1 mm squares were made on the coating film, and an adhesion test of the hard coat layer was performed using cellophane tape. In this test, the peeling state of the squares was observed, and the number of remaining squares was counted. The results are shown in Table 5. [Table 5] The components of the various topcoats in Table 5 are as follows: Water-based UV top coat A: 250 g (Net 50 g) of water-based urethane acrylate UAW-1000W20 (Kyoeisha Chemical Co., Ltd.) was mixed with 50 g of dimethylacrylamide (DMAA) and 4 g of photopolymerization initiator Irgacure 2959 (solid content 34%). Solvent-free UV top coat B: NSX-201F-NS, manufactured by Kyoeisha Chemical Co., Ltd., contains photopolymerization initiator, Solvent-based UV top coat C: 100 g of urethane acrylate UA-P300, manufactured by Kyoeisha Chemical Co., Ltd., was mixed and dissolved in 100 g of organic solvent (MEK / MIBK=1 / 1) and 4 g of photopolymerization initiator Omnirad184 (solid content 50%). [Industrial Applicability]

[0041] The production method for the water-dispersible adhesive composition and the water-dispersible adhesive composition of the present invention can be used as an easily adhesive polyester film, a coated article, and the like, mainly for touch panel films for personal computers, mobile devices, car navigation systems, and the like, displays for computers, televisions, liquid crystal display devices, and the like, kitchen cabinets, and the front surfaces of decorative materials around vanity sinks, and the like.

Claims

1. reacting 1 mole of an isocyanate compound having (m+n) isocyanate groups with n moles of a hydroxyl group-containing (meth)acrylate compound; Next, the resulting reaction product is reacted with an alkylene oxide (meth)acrylate adduct or a polyalkylene glycol compound having a hydroxyl group at one end in an amount of m moles, Obtaining a urethane (meth)acrylate oligomer represented by formula (1), While adding water to the urethane (meth)acrylate oligomer, the interface between the urethane (meth)acrylate oligomer and the water is gently stirred at 100 rpm to 200 rpm to emulsify the mixture, thereby preparing a water-soluble urethane (meth)acrylate oligomer composition; A method for producing a water-dispersible adhesive composition, comprising adding a water-soluble polyester resin and a crosslinking agent to the water-soluble urethane (meth)acrylate oligomer composition in a solid content ratio of 100 parts by mass of the water-soluble urethane (meth)acrylate oligomer composition:water-soluble polyester resin and crosslinking agent:50 parts by mass to 150 parts by mass, and in a solid content ratio of 62.5 parts by mass / 37.5 parts by mass to 90 parts by mass / 10 parts by mass. (R 1 O-CONH) m -R 2 -(NHCO-OR 3 ) n (1) (In the formula, R 1 O- represents a dehydrogenation residue of a polyalkylene glycol compound having a hydroxyl group at one end or a (meth)acrylic acid alkylene oxide adduct; R 2 represents a residue of a deisocyanated group of an isocyanate compound, -OR 3 represents a dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound, m and n each represent an integer between 1 and 50, provided that m≦n.

2. 2. The method according to claim 1, wherein the stirring is carried out using a paddle blade at a rotation speed of 100 rpm to 200 rpm.

3. 3. The method according to claim 1, wherein the water is added until the solid content becomes 50% by mass or less, and after the addition of the water is completed, gentle stirring is continued for a predetermined period of time.

4. The method according to claim 3, wherein after the addition of the water is completed, stirring is continued for 10 minutes or more at a rotation speed of 100 rpm to 200 rpm.

5. The method according to any one of claims 1 to 4, wherein the isocyanate compound is a diisocyanate or a polyisocyanate of a diisocyanate monomer.

6. The method according to any one of claims 1 to 5, wherein the polyalkylene glycol compound containing a hydroxyl group at one end is an alkoxy polyalkylene glycol.

7. The method according to any one of claims 1 to 6, wherein the (meth)acrylic acid alkylene oxide adduct compound is a compound obtained by adding (meth)acrylic acid to an alkylene oxide or by mono(meth)acrylate of a polyalkylene glycol.

8. The method according to any one of claims 1 to 7, wherein the hydroxyl group-containing (meth)acrylate compound is a hydroxyalkyl (meth)acrylate, a polyol (meth)acrylate or an alkylene oxide-added polyol (meth)acrylate.

9. 9. An active energy ray-curable water-dispersible adhesive composition comprising the water-dispersible adhesive composition obtained by the method according to claim 1 and a photopolymerization initiator.

10. A highly adhesive polyester film comprising a polyester film and a layered cured product of the water-dispersible adhesive composition according to claim 9 laminated on the polyester film.

11. The highly adhesive polyester film according to claim 10, further comprising a hard coat layer laminated on the layered cured product.

12. Coating object and A coated article comprising a cured product of the active energy ray-curable water-dispersible adhesive composition according to claim 9 disposed on the surface of the substrate.

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