JP2006182871A - Active energy ray-curing type water-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curing type water-based resin composition having little environmental pollution, excellent in preservation stability, highly sensitive to energy rays and giving practical coating film strength in a short time. <P>SOLUTION: The active energy ray-curing type water-based resin composition contains a water-dispersive polyurethane inner salt prepared by dispersing, in water, a reaction product obtained by reacting (a) a polyhydroxy compound having at least one optically reactive onium group bonded to a chromophore through a bonding group and ≥2 hydroxy groups with (b) a polyhydroxy compound having at least one sulfonate group and ≥2 hydroxy groups as essential ingredients. The active energy ray-curing type water-based resin composition also contains a water-dispersive polyurethane prepared by dispersing, in water, a reaction product obtained by reacting the compound (a), the compound (b) and a compound (c) having at least one unsaturated double bond and at least one hydroxy group as essential ingredients, and a photoinitiator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is an aqueous resin composition that is cured by irradiation with active energy rays, particularly ultraviolet rays, and further is an aqueous resin composition that is aqueous but forms a hydrophobic coating after curing, and has excellent durability. The present invention relates to an active energy ray-curable aqueous resin composition useful as a binder for paints, printing inks, ink jet recording inks, adhesives, coating materials and the like.

  Since the active energy ray-curable resin does not substantially contain an organic solvent, it is excellent in safety and hygiene of the working environment during use in coating and printing. Furthermore, it is expected to be a non-polluting resin composition for paints, inks, and coating materials because it has a high curing speed and is advantageous from the viewpoint of productivity improvement and energy saving. Conventional organic solvent-based paints, inks, and coating materials Instead, the field of practical application is gradually expanding.

However, since the conventional active energy ray-curable resin composition is generally high in viscosity, a large amount of a reactive diluent or an organic solvent is used in combination for adjusting coating viscosity and rheological properties. This is the current situation. When a large amount of reactive diluent is used, it causes problems such as skin irritation, hypersensitivity disorder, reduced curability, and reduced physical properties of the cured product such as hardness. The risk of fire is high, and it is not preferable for occupational health.

  The active energy ray curable aqueous resin composition solves the problems of high viscosity, safety and hygiene, which are the disadvantages of the conventional active energy ray curable resin composition described above, as well as comprehensive coating. In recent years, it has attracted much attention because it can improve performance and reduce costs of raw materials.

  Examples of active energy ray-curable aqueous resin compositions that have been proposed so far are: 1. Water-soluble resin type 2. Emulsion type 3. Colloidal dispersion type There are forced emulsification types. Among these, typical materials include urethane acrylate dispersions to which the above two types belong. This urethane acrylate dispersion is generally excellent in coating suitability and coating film performance as compared with other water-soluble resin types, emulsion types, and forced emulsification types.

  The urethane acrylate dispersion can be synthesized by a known method. By reacting a diisocyanate, a diol, and a diol containing a carboxylic acid to prepare a carboxyl group-containing polyurethane oligomer having an isocyanate group at the end, then reacting a hydroxy group-containing acrylic monomer, and dispersing in water after neutralization An aqueous dispersion of urethane acrylate containing an unsaturated double bond at the molecular end is obtained.

  In the coating composition based on the urethane acrylate dispersion according to the prior art, the carboxylate or carboxylic acid, which is essential for water dispersion, is present after curing. There is a problem that durability such as water resistance of the coating film obtained is insufficient. An object of the present invention is to provide an active energy ray-curable aqueous resin composition that provides excellent durability after curing by irradiation with active energy rays, which is difficult to achieve with the prior art.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyhydroxy compound having at least one photoreactive onium group and two or more hydroxyl groups bonded to a chromophore via a bonding group, ( b) a reaction obtained by reacting, as essential components, a polyhydroxy compound having at least one sulfonate group and two or more hydroxyl groups, and (c) a polyisocyanate compound having two or more isocyanate groups in one molecule. By using a water-dispersible polyurethane inner salt in which the product is dispersed in water, it has been found that problems that could not be achieved conventionally can be achieved, and the present invention has been completed.

The photoreactive onium group bonded to the chromophore via the linking group reacts with the nucleophilic sulfonate anion upon irradiation with active energy rays to form a cross-linked structure and at the same time to lose the ionicity of the onium group. , Convert to hydrophobic. A polymer containing a photoreactive onium group bonded to a chromophore through such a linking group and an anionic group such as carboxylate, alkoxide, or phenoxide is water-soluble, has photocurability, and is hydrophobic after curing. Conversion to gender is described in JP-T-8-509820 and JP-T-9-501609. However, these polymers have a problem that the sensitivity to active energy rays is too low. Therefore, after intensive studies, polyurethanes containing photoreactive onium groups and sulfonate groups at the same time as internal salts are highly sensitive to active energy rays, exhibit stable water dispersibility, and are coated with active energy rays. It has been found that the film is excellent in water resistance, adhesion and chemical resistance. These polyurethane emulsions and dispersions have not been reported so far, and the active energy ray-curable aqueous resin composition of the present invention is a novel material.

That is, the present invention relates to (a) a polyhydroxy compound having at least one photoreactive onium group and two or more hydroxyl groups bonded to the chromophore via a linking group, and (b) at least one sulfonate group. Water in which a reaction product obtained by reacting a polyhydroxy compound having two or more hydroxyl groups and (c) a polyisocyanate compound having two or more isocyanate groups in one molecule as an essential component is dispersed in water An active energy ray-curable aqueous resin composition comprising a dispersible polyurethane inner salt, and (a), (b), (c) and (d) at least one unsaturated double bond And a reaction product obtained by reacting a compound having at least one hydroxyl group as an essential component with water. An active energy ray-curable aqueous resin composition comprising a water-dispersible polyurethane inner salt and a photopolymerization initiator, and a compound having two or more unsaturated double bonds in the molecule The present invention further relates to an active energy ray-curable aqueous resin composition.

  Since the active energy ray-curable resin group of the present invention contains an onium group cation and a sulfonate anion which are hydrophilic groups, it is a self-emulsifiable and stable aqueous dispersion. And since the photoreactive onium group cation and the sulfonate group anion are converted to a hydrophobic group simultaneously with the formation of a crosslinked structure by irradiation with active energy rays, the obtained cured coating film has no or few hydrophilic groups, Moreover, in order to form a crosslinked structure, a coating film excellent in water resistance, abrasion resistance and chemical resistance can be formed. For this reason, it can be set as a useful aqueous binder composition with little environmental pollution.

Hereinafter, the active energy ray-curable aqueous resin composition of the present invention will be described in detail. The water-dispersible polyurethane of the present invention is produced, for example, by the following method. First, (a) a polyhydroxy compound having at least one photoreactive onium group and two or more hydroxyl groups bonded to the chromophore via an linking group in an organic solvent, (b) at least one sulfonate group And a polyhydroxy compound having two or more hydroxyl groups and (c) a polyisocyanate compound having two or more isocyanate groups in one molecule, and a prepolymer having an isocyanate group at the terminal is produced, The terminal isocyanate group is reacted with (d) a compound having at least one unsaturated double bond and at least one hydroxyl group to react the active isocyanate group as an essential component for sealing. Subsequently, it is converted into an O / W type emulsion by adding water. Subsequently, the water-dispersible urethane is obtained by recovering the organic solvent and a part of the water under reduced pressure. Furthermore, a water-dispersible urethane internal salt can be obtained by internal salification by a known method of contacting an appropriate ion exchange resin.

Preferable specific examples of the polyhydroxy compound having at least one photoreactive onium group and two or more hydroxyl groups bonded to the chromophore through a bonding group used in the present invention include bisphenol A diglycidyl ether and Reaction products with onium precursors such as trialkylamines, dialkissulfides, and trialkylphosphines can be mentioned. Further, the counter anion associated with the photoreactive onium group is selected so as not to inhibit the reaction between the photoreactive onium group and the sulfonate when irradiated with active energy rays. The onium group counter anion can be converted to the desired counter anion by contacting it with a suitable ion exchange resin in a conventional manner. A preferred counter anion is a bicarbonate anion.

The amount of the onium group of the present invention is 30 to 3000 mmol / wt based on the dry weight of the active energy ray-curable aqueous resin composition in consideration of water solubility or self-emulsifying property, durability of the cured coating film and light sensitivity. kg, preferably 50 to 2000 mmol / kg, more preferably 80 to 2000 mmol / kg.

A preferred specific example of the polyhydroxy compound having at least one sulfonate group and two or more hydroxyl groups used in the present invention is a diol containing sodium phenylsulfonate. For example, 5-sulfoisophthalic acid dimethyl sodium salt was reacted with 4 mol of diethylene glycol at 150 ° C. and further reacted with ε-caprolactone to obtain sodium phenylsulfonate-containing polycaprolactone diol. After polyurethane synthesis, sodium can be easily removed by contacting with an appropriate ion exchange resin.

  The amount of the sulfonate group of the present invention is basically preferably the same mole as the photoreactive onium group in order to internally salify with the photoreactive onium group cation, but the molar ratio may be changed as necessary. You can also.

  Examples of the polyisocyanate compound having two or more isocyanate groups in one molecule used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate and other aromatic diisocyanates, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. Examples of the aliphatic or alicyclic diisocyanate and hexamethylene diisocyanate include triisocyanate such as cyclic trimer. However, it is not limited to these.

  Examples of the compound having at least one unsaturated double bond and at least one hydroxyl group used in the present invention include the following. Suitable compounds having a hydroxyl group and at least one unsaturated double bond are hydroxyalkyl (meth) such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Examples include acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate. In order to introduce two or more unsaturated double bonds, polyvalents such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. Examples include poly (meth) acrylates of alcohol. With suitable polyols having at least two hydroxyl groups, unsaturated double bonds can be incorporated not only at the ends of the polyurethane chain but also at the side chains of the polymer backbone. Suitable compounds for this purpose include glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, and pentaerythritol di (meth) acrylate.

  In the production of the water dispersible polyurethane inner salt of the present invention, a high molecular weight or low molecular weight polyol, preferably a diol, is used in order to control physical properties such as film forming property and elastic modulus of the cured coating film. . Examples of preferred polyols include polyester polyols and hexamethylene carbonates selected from esters of polyhydric alcohols and polybasic acids. Polycarbonate diols such as pentamethylene carbonate, polyether diols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polylactone diols such as polycaprolacton diol and polybutyrolactone diol, and polyhydroxy olefins.

  The photopolymerization initiator used in the present invention is not particularly limited as long as it is a substance having a function capable of initiating vinyl polymerization by irradiation with active energy rays. Specific examples include 2,2-dimethoxy-diphenylmethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphos Fin oxide, 1- [4-2-2- (hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, iron allene complex, benzoin, benzyldimethyl ketal, 2,4,6-trimethyl Benzophenone, 4-methylbenzophenone, 2-isopropylidhioxanthone, 4-i Like propyl thioxanthone, but it is not particularly limited thereto.

  The blending amount of the photopolymerization initiator is preferably 0 to 10% by weight based on the dry weight of the water-dispersible polyurethane inner salt and the compound having two or more unsaturated double bonds in the molecule.

  As the compound having two or more unsaturated double bonds in the molecule used in the present invention, (meth) acrylate oligomers generally used in UV curable paints, inks, resists, etc. are used. it can. Among these, preferred are tri (meth) acrylates of trimethylol proman propylene oxide 3 mol adduct, triacrylates of trimethylol proman ethylene oxide 3 mol adduct, dipentaerythritol penta (meth) acrylate, and the like. Polyfunctional (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, unsaturated oligomers such as diallyl phthalate, unsaturated polyester, etc. However, it is not limited to these.

  The compounding amount of the compound having two or more unsaturated double bonds in the molecule is preferably 0 to 50% by weight based on the dry weight of the water-dispersible polyurethane inner salt.

  The active energy ray-curable aqueous resin composition of the present invention may further comprise barium sulfate, barium titanate, silicon oxide powder, finely divided silicon, and amorphous silica for the purpose of further improving properties such as adhesion and hardness. Well-known inorganic fillers such as talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, and mica powder can be used. The amount to be used is preferably 0 to 60% by weight, particularly preferably 5 to 40% by weight in the composition of the present invention.

Color materials such as coloring pigments and dyes can be used as necessary. Examples of the coloring pigment include the following. Examples of yellow pigments include Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 55, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 128, and 138. 139, 150, 151, 154 and 180. Examples of the magenta pigment include Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57: 1, 57 (Sr), 57: 2, 122, 123, 168, 184, 202, 238 and the like. be able to. Examples of cyan pigments include pigment blue 1, 2, 3, 13, 15, 16, 22, 60, and bat blue 4 and 60. Carbon black can be suitably used as the black pigment.

  As the dye, a cationic dye can be preferably used as follows. As basic dyes in the present invention, acridine, methine, polymethine, azo, azomethine, xanthene, thioxanthene, oxazine, thioxazine, triallylmethane, cyanine, anthraquinone, phthalocyanine, etc. A known basic dye can be used. Especially for the three primary colors of the process color, C.I. I. Basic Yellow 11, 12, 13, 21, 23, 24, 33, 40, 51, 54, 63, 71, 87 are C.I. I. Basic Red 13, 14, 45, 19, 26, 27, 34, 35, 36, 38, 39, 42, 43, 45, 46, 50, 51, 52, 53, 56, 59, 63, 65, 66, 71, C.I. I. Basic Violet 7, 11, 14, 15, 16, 18, 19, 20, 28, 29, 30, 33, 34, 35, 36, 38, 39, 41, 44 are C.I. I. Basic Blue 3, 22, 33, 41, 45, 54, 63, 65, 66, 67, 75, 77, 85, 87, 88, 109, 116 are preferably used.

  As a special example of the color material, polymer fine particles colored with a dye can be used. More specifically, anionic group-containing polymer fine particles dyed with a cationic dye, acid dyes, cationic group-containing polymers dyed with direct dyes, or polymer particles colored with oily dyes, disperse dyes, etc. are used. It is possible.

Furthermore, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tertiary-butylcatechol, pyrogallol, phenothiazine, etc., known thickeners such as asbestos, olben, benton, montmorillonite, antifoaming agents such as silicones, fluorines, and polymers Alternatively, known additives such as leveling agents, imidazole-based, thiazole-based, triazole-based, and adhesion-imparting agents such as silane coupling agents can be used. Further, known binder resins such as forced dispersions of other photopolymerizable oligomers, double bond-containing aqueous acrylic resins, other aqueous urethane resins, and aqueous acrylic resins can be mixed and used within an appropriate range.

  The medium of the composition of the present invention is basically water. Furthermore, the aqueous medium obtained by adding a water-soluble organic compound to water as needed can be used suitably. The water-soluble organic compound is mainly used for imparting non-volatility to the composition, reducing the viscosity, and ensuring the wettability of the composition to the substrate to be coated, and is suitable for such purpose. Anything can be used. When the substrate to be coated is non-absorbable, the aqueous medium is formed only with water, or when a water-soluble organic solvent is used, the aqueous medium is easily evaporated, or all of the aqueous medium is a cured film. It is preferable that it is taken in.

  Examples of water-soluble organic compounds include methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, sepanol, C8 or higher alcohols, ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, 1,2,4-butane. Triol, 1,2,6-hexanetriol, 1,2,5-pentanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dimethyl sulfoxide, diacetone alcohol, glycerin mono Allyl ether, propylene glycol, butylene glycol, polyethylene glycol 300, thiodiglycol, N-methyl-2-pyrrolidone, 2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl 2-Imidazolidinone, sulfolane, trimethylolpropane, trimethylolethane, neopentyl glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, β-dihydroxyethyl urea, urea, acetonyl acetone, pentaerythritol, 1,4-cyclohexanediol, hexylene Glycol, ethylene glycol mono Propyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetra Ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl Ether, glycerol monoacetate, glycerol diacetate, glycerol triacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, cyclohexanol, 1,2-cyclohexanediol, 1-butanol, 3-methyl-1,5-pentanediol, 3 -Hexene-2,5-diol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, monoethanolamine, diethanolamine, triethanolamine, etc. These can be used alone or in combination of two or more.

  The composition of this invention can be prepared by mix | blending a required component in an aqueous medium. The order of mixing the components is not particularly limited. However, it is preferable that the mixing be performed quickly without maintaining a non-uniform state for a long time.

  The composition of the present invention can be formed into a coating film by a conventional method such as brush coating, spray coating, curtain coating, monocoating, spin coating, screen printing, gravure printing, flexographic printing, inkjet printing or the like. As the processing apparatus, those having a structure in which an active energy ray irradiation apparatus is mounted on these coating machines can be suitably used.

  The active energy ray is irradiated from the upper part or the lower part to the coating surface of the coating machine agent that has left the coating part. In the case of a transparent substrate to be coated, irradiation from both above and below is effective as necessary. The time interval from application to irradiation area must be adjustable by the amount of moisture contained in the composition. It is also possible to install a mechanism for heating and drying between the application area and the active energy ray irradiation apparatus.

  As an active energy ray source used for the irradiation device, a so-called low-pressure mercury lamp whose mercury vapor pressure is 1 to 10 Pa during lighting, a high-pressure mercury lamp having a higher pressure, or an ultra-high-pressure mercury lamp having a higher pressure. Further, a mercury lamp coated with a phosphor, a laser, a fluorescent tube, a cold cathode tube, other discharge tubes, and the like can be used. In particular, a mercury lamp is practically preferable. The emission spectrum of the active energy ray region of the mercury lamp is in the range of 184 to 450 nm, which is suitable for efficiently reacting the active energy ray polymerizable compound in the composition. As mercury lamps, metal halide lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon flash lamps, deep UV lamps, UV lasers, etc. have been put into practical use, and the emission wavelength range includes the above range, so the power supply size, input intensity, It can be appropriately selected and used according to the lamp shape and the like. The light source is preferably selected in consideration of suitability with the absorption wavelength of the curable composition. In the active energy ray-curable aqueous resin composition of the present invention, when the reactive onium group is a benzylonium group and / or a naphthylmethyleneonium group, a mercury lamp that oscillates ultraviolet rays having a wavelength of 200 to 300 nm is particularly preferable.

The necessary active energy ray intensity is desirable for obtaining a better polymerization rate when the total energy in the ultraviolet region is about 1 to 1000 mW / cm ² . The irradiation time is practically in the range of 0.1 to 100 seconds. If the integrated irradiation amount is insufficient, the adhesive force of the fixed composition to the substrate to be coated may not be sufficient, and it is preferable to perform the irradiation treatment in consideration of the necessary integrated irradiation amount. By fixing the composition with active energy rays and fixing it to the substrate to be coated, good fixing, scratching, water resistance and the like can be obtained. At the same time, deformation of the substrate to be coated itself, such as curling and cockle, is also suppressed, and handling and storage can be improved.

(Function)
The active energy ray-curable composition of the present invention has a self-emulsifying property because it contains a photoreactive onium group, which is a hydrophilic group, and an internal salt of a sulfonate group. In addition, since the onium group and the sulfonate group react with each other by irradiation with active energy rays and are converted to hydrophobic groups in order to lose ionicity, a crosslinking reaction also takes place at the same time. There is no or little and a strong cross-linked structure is formed. Therefore, a coating film excellent in water resistance, abrasion resistance, and chemical resistance can be formed.

Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis example 1
Synthesis of diol 1 (containing ammonium group) In a 500 ml three-necked flask equipped with a mechanical stirrer, reflux condenser, and nitrogen gas bubbler, 10.3 g of bisphenol A diglycidyl ether (epoxy equivalent 190), Dimethyl monoethanolamine 5.5 g, glacial acetic acid 3.5 ml and a solvent tetrahydrofuran 175 ml were added. The solution was stirred at 50 ° C. for about 50 hours, then cooled, and the solvent was removed with an evaporator to obtain diol 1.

Synthesis example 2
Synthesis of diol 2 (containing sulfonium group) In a 500 ml three-necked flask equipped with a mechanical stirrer, reflux condenser, and nitrogen gas bubbler, 10.3 g of bisphenol A diglycidyl ether (epoxy equivalent 190), 3.7 g of dimethyl sulfide, 5 ml of acetic acid and 175 ml of tetrahydrofuran as a solvent were added. The solution was stirred at 50 ° C. for about 50 hours, then cooled, and the solvent was removed with an evaporator to obtain diol 2.

Synthesis example 3
Synthesis of diol 3 (containing phosphonium group) In a 500 ml three-necked flask equipped with a mechanical stirrer, reflux condenser and nitrogen gas bubbler, 10.3 g of bisphenol A diglycidyl ether (epoxy equivalent 190), 120 g of tri (n-butyl) phosphine, 5 ml of acetic acid and 175 ml of tetrahydrofuran as a solvent were added. The solution was stirred at 50 ° C. for about 50 hours and then heated at reflux temperature for 2 days. After cooling, the solvent was removed with an evaporator to obtain diol 3.

Synthesis example 4
Synthesis of diol 4 (containing sodium phenylsulfonate) Sodium salt of dimethyl 5-sulfoisophthalate 201 g (0.68 mol), diethylene glycol 286.6 g (2.7 mol), zinc acetate 0.49 g (2.7 mmol) Were mixed and reacted at 150 ° C. for 10 hours. After distilling off the liberated methanol and cooling to room temperature, 1038 g (9.2 mol) of ε-caprolactone and 0.89 g (1.4 mmol) of dibutyltin dilaurate were added and reacted at 150 ° C. for 6 hours. After cooling to room temperature, the product was gradually crystallized to obtain solid diol 4 (molecular weight 600).

Synthesis example 5
Polyurethane dispersion 1
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850), 63 of Diol 1 0.7 g, 60 g of diol 4, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. with stirring in the air and dissolved uniformly. Subsequently, 122 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was then added to cation exchange resin (Amberlite IR120B) in which the counter cation was exchanged with proton using 2000 ml of hydrochloric acid in advance and stirred for about 1 day. The cation exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. Further, it was added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. The filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. The polyurethane dispersion 1 was obtained by adding% by weight.

Synthesis Example 6
Polyurethane dispersion 2
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850) and 63 of diol 1 were prepared. 0.7 g, 60 g of diol 4, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. with stirring in the air and dissolved uniformly. Subsequently, 142 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 23 g of 2-ethylhexyl acrylate was added to the reaction mixture, and the reaction was continued at 90 ± 5 ° C. for another 2 hours. The reaction mixture was cooled to 65 ° C., 5.5 g of photoinitiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added, and stirring was continued for 30 minutes. Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was then added to cation exchange resin (Amberlite IR120B) in which the counter cation was exchanged with proton using 2000 ml of hydrochloric acid in advance and stirred for about 1 day. The cation exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. Further, it was added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. The filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. The polyurethane dispersion 2 was obtained by adding% by weight.

Synthesis Example 6
Polyurethane dispersion 3
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850) and 58 of diol 2 were mixed. .3 g, 60 g of diol 4, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. while stirring in the air and dissolved uniformly. Subsequently, 122 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was then added to cation exchange resin (Amberlite IR120B) in which the counter cation was exchanged with proton using 2000 ml of hydrochloric acid in advance and stirred for about 1 day. The cation exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. Further, it was added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. The filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. % By weight was added to obtain a polyurethane dispersion 3.

Synthesis example 7
Polyurethane dispersion 4
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850) and 58 of diol 2 were mixed. .3 g, 60 g of diol 4, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. while stirring in the air and dissolved uniformly. Subsequently, 142 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 23 g of 2-ethylhexyl acrylate was added to the reaction mixture, and the reaction was continued at 90 ± 5 ° C. for another 2 hours. The reaction mixture was cooled to 65 ° C., 5.5 g of photoinitiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added, and stirring was continued for 30 minutes.
Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was then added to cation exchange resin (Amberlite IR120B) in which the counter cation was exchanged with proton using 2000 ml of hydrochloric acid in advance and stirred for about 1 day. The cation exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. Further, it was added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. This filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. The polyurethane dispersion 4 was obtained by adding% by weight.

Synthesis example 8
Polyurethane dispersion 5
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850) and 86 of diol 3 were prepared with the following composition. .3 g, 60 g of diol 4, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. while stirring in the air and dissolved uniformly. Subsequently, 122 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was then added to cation exchange resin (Amberlite IR120B) in which the counter cation was exchanged with proton using 2000 ml of hydrochloric acid in advance and stirred for about 1 day. The cation exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. Further, it was added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. The filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. The polyurethane dispersion 5 was obtained by adding% by weight.

Synthesis Example 9
Polyurethane dispersion 6
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850) and 86 of diol 3 were prepared with the following composition. .3 g, 60 g of diol 4, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. while stirring in the air and dissolved uniformly. Subsequently, 142 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 23 g of 2-ethylhexyl acrylate was added to the reaction mixture, and the reaction was continued at 90 ± 5 ° C. for another 2 hours. The reaction mixture was cooled to 65 ° C., 5.5 g of photoinitiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added, and stirring was continued for 30 minutes.
Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was then added to cation exchange resin (Amberlite IR120B) in which the counter cation was exchanged with proton using 2000 ml of hydrochloric acid in advance and stirred for about 1 day. The cation exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. Further, it was added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. The filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. The polyurethane dispersion 6 was obtained by adding% by weight.

Synthesis Example 10
Polyurethane dispersion 7
A polyurethane water dispersion was obtained in the same manner as in Synthesis Example 5, except that the polyurethane dispersion 7 was obtained without the treatment with a cation exchange resin and the treatment with an anion exchange resin.

Synthesis Example 11
Polyurethane dispersion 8
Into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet and a stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850) and 63 of diol 1 were prepared. 0.7 g, 13.3 g of dimethylolpropionic acid, 0.35 g of hydroquinone, and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. with stirring in the air and dissolved uniformly. Subsequently, 122 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 565 g of ion-exchanged water was added, and then ethyl acetate was distilled off under reduced pressure. Further, this aqueous solution was further added to 2000 ml of an anion exchange resin (Amberlite IRA400J) in which the counter anion was exchanged with the bicarbonate anion using sodium bicarbonate in advance and stirred for about 1 day. The anion exchange resin was filtered off, the resin was further washed with water / t-butanol, and the filtrate was collected. The filtrate was evaporated at a vacuum degree of 60 mmHg or more, further diluted with water to a solid content of 25%, and then wet modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) 0.1. The polyurethane dispersion 8 was obtained by adding% by weight.

Synthesis Example 12
Polyurethane dispersion 9
In a four-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet and stirrer, 293 g of polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG-850SN, molecular weight 850), dimethylolpropionic acid 26.6 g, 50 g of polybutyrolactone diol (molecular weight 500), 0.35 g of hydroquinone and 150 g of ethyl acetate were added, and the mixture was heated to 90 ° C. with stirring in the air and dissolved uniformly.
Subsequently, 122 g of isophorone diisocyanate, 0.9 g of organotin catalyst KS-1260 (manufactured by Kyodo Yakuhin Co., Ltd.) and 0.2 g of amine catalyst U-CAT-SA102 (manufactured by San Apro Co., Ltd.) were added, and 90 ± The reaction was performed at 5 ° C. for 2 hours. Subsequently, 21 g of triethylamine was added, 565 g of ion-exchanged water was further added, and then ethyl acetate was distilled off under reduced pressure. After adding water and diluting to a solid content of 25%, 0.1% by weight of a wetting modifier Polyflow KL-260 (manufactured by Kyoeisha Chemical Co., Ltd.) was added to obtain a polyurethane dispersion 9.

Example 1
Polyurethane aqueous dispersion 1 was applied to a cold-rolled steel sheet with a bar coater so as to have a dry film thickness of 4 g / m ^2, and then dried at 80 ° C. for 2 minutes. This film was cured by irradiating ultraviolet rays with a sterilizing lamp (oscillation peak wavelength 254 nm), and then various tests were performed.

Examples 2-6
Except for using polyurethane dispersions 2 to 6 instead of polyurethane dispersion 1, the same operation as in Example 1 was performed to obtain a cured film for testing.

Comparative Examples 1-3
Except for using the polyurethane dispersions 7 to 9 instead of the polyurethane dispersion 1, the same operation as in Example 1 was performed to obtain a cured film and tested.

  Table 1 shows the composition of each composition.

Each test method is as follows.

(1) Adhesiveness The sample irradiated with a predetermined amount of light was evaluated by a cello tape (registered trademark) peeling test based on K5600-5-6 adhesion (cross-cut method) in the JIS coating film evaluation method.
(2) Water resistance A sample subjected to a predetermined amount of light irradiation was immersed in water at 80 ° C. for 1 hour and taken out, and then the above-mentioned adhesion test was performed to evaluate water resistance.
(3) Chemical resistance Ethyl acetate was soaked in gauze, and a rubbing test was performed by rubbing the surface of a sample irradiated with a predetermined amount of light using this gauze, and changes in the appearance of the coating film were observed. The evaluation results were expressed as follows.
Evaluation criteria;
◎: Very good ○: Good △: Slightly bad ×: Poor

The obtained evaluation results are shown in Table 2.

From the above results, the coating film of the active energy ray-curable composition based on polyurethane containing the photoreactive onium group bonded to the chromophore through a bonding group as a hydrophilic group and a sulfonate group as an internal salt is obtained by ultraviolet irradiation. It can be seen that the adhesiveness, water resistance, and chemical resistance of the coating film are clearly excellent and high sensitivity.

  The aqueous active energy ray-curable composition of the present invention has high sensitivity to active energy rays, can form a coating film excellent in water resistance and abrasion resistance while being aqueous, and is an ink for image recording or the like. It can be expected to be used as a useful aqueous binder composition with less environmental pollution in applications such as coating agents and coating agents.

Claims (3)

(1) (a) a polyhydroxy compound having at least one photoreactive onium group and two or more hydroxyl groups bonded to the chromophore via a linking group, (b) at least one sulfonate group and two Water-dispersible polyurethane in which a reaction product obtained by reacting the above-mentioned polyhydroxy compound having a hydroxyl group and (c) a polyisocyanate compound having two or more isocyanate groups in one molecule as an essential component is dispersed in water. An active energy ray-curable aqueous resin composition comprising an internal salt. (1) (a) a polyhydroxy compound having at least one photoreactive onium group and two or more hydroxyl groups bonded to the chromophore via a linking group, (b) at least one sulfonate group and two A polyhydroxy compound having the above hydroxyl groups, (c) a polyisocyanate compound having two or more isocyanate groups in one molecule, and (d) having at least one unsaturated double bond and at least one hydroxyl group. An active energy ray-curable aqueous resin composition comprising a water-dispersible polyurethane inner salt in which a reaction product obtained by reacting a compound as an essential component is dispersed in water and (2) a photopolymerization initiator . The active energy ray-curable aqueous resin composition according to claim 2, further comprising a compound having two or more unsaturated double bonds in the molecule.