Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates

Definitions

• the present invention relates to an active energy ray-curable composition useful as a raw material for paints, inks and the like. Furthermore, the present invention relates to an active energy ray curable coating and an active energy ray curable printing ink using the composition.
• Active energy ray-curable composition has a low heat history on the coated substrate and is excellent in coating film hardness and scratch resistance.
• hard coating agents for various plastic substrates such as home appliances and mobile phones, paper, etc. It is used in various fields such as overcoat agent, binder for printing ink, solder resist.
• an epoxy acrylate resin obtained by adding acrylic acid or methacrylic acid to an epoxy resin has been widely used in various fields as a material excellent in adhesion and adhesion to a base material (for example, see Patent Document 1).
• the problem to be solved by the present invention is that it can impart excellent scratch resistance when used in paints such as hard coat agents, and has excellent misting resistance when used in printing ink. It is providing the active energy ray-curable composition which can provide adhesiveness and solvent resistance. Moreover, it is providing the active energy ray-curable coating material and active energy ray-curable printing ink using this active energy ray-curable composition.
• the present inventors reacted polyfunctional acrylate, aromatic dicarboxylic acid, and aromatic epoxy resin, and then obtained polymerizable product was polymerized.
• An active energy ray-curable composition obtained by reacting a carboxylic acid having an unsaturated group can impart high scratch resistance to the cured coating film when used in a coating material such as a hard coating agent, and printing.
• the inventors When used in inks, the inventors have found that the inks can be provided with high misting resistance, and that the cured coating film can be provided with high adhesion to the substrate and high solvent resistance, and the present invention has been completed.
• a polyfunctional acrylate (A), an aromatic dicarboxylic acid (B), and an aromatic epoxy resin (C) are reacted, and then a polymerizable unsaturated group is added to the obtained reaction product.
• the present invention relates to an active energy ray-curable composition obtained by reacting a carboxylic acid (D) having an active energy ray-curable composition, an active energy ray-curable coating material and an active energy ray-curable printing ink using the composition.
• the active energy ray-curable composition of the present invention when used in a paint such as a hard coat agent, can impart high scratch resistance to the cured coating film, so that home appliances such as televisions, refrigerators, washing machines, air conditioners, etc.
• home appliances such as televisions, refrigerators, washing machines, air conditioners, etc.
• Housing of products Housing of electronic devices such as personal computers, smartphones, mobile phones, digital cameras and game machines; Interior materials of various vehicles such as automobiles and railway vehicles; Various building materials such as decorative panels; Woodworking materials such as furniture; Artificial / synthetic leather; useful as a material for hard coat agents that form a protective film on the surface of articles such as FRP bathtubs.
• the active energy ray-curable composition of the present invention when used in printing ink, can impart high misting resistance to the ink, and the cured coating film has high adhesion to the substrate and high solvent resistance. Therefore, it is useful as a binder for various printing inks such as lithographic inks and gravure inks.
• the active energy ray-curable aqueous resin composition of the present invention is obtained by reacting a polyfunctional acrylate (A), an aromatic dicarboxylic acid (B), and an aromatic epoxy resin (C), and then the obtained reaction product. And a carboxylic acid (D) having a polymerizable unsaturated group.
• the polyfunctional acrylate (A) is a compound having two or more acryloyl groups, and the number of acryloyl groups is preferably three.
• the compound having three acryloyl groups include trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, and glycerin propoxytriacrylate.
• these polyfunctional acrylates (A) ethylene oxide-modified trimethylolpropane triacrylate is preferable.
• these polyfunctional acrylates (A) can be used alone or in combination of two or more.
• the aromatic dicarboxylic acid (B) is a dicarboxylic acid having an aromatic ring.
• the aromatic dicarboxylic acid (B) include phthalic acid, isophthalic acid, terephthalic acid, and the like.
• anhydrides of aromatic dicarboxylic acids such as phthalic anhydride and trimellitic anhydride can also be used.
• isophthalic acid is preferable because of its high reactivity with the epoxy group of the aromatic epoxy resin.
• these aromatic dicarboxylic acids (B) can be used alone or in combination of two or more.
• the aromatic epoxy resin (C) is an epoxy resin having an aromatic ring.
• the aromatic epoxy resin (C) include biphenol type epoxy resins such as tetramethylbiphenol type epoxy resins; bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; Dicyclopentadiene-modified aromatic bifunctional epoxy resin; dihydroxynaphthalene type epoxy resin obtained by epoxidizing dihydroxynaphthalene; glycidyl ester type resin of aromatic dicarboxylic acid; bifunctional epoxy resin derived from xylenol, naphthalene aralkyl Epoxy resins; epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dicyclopentadiene; ester-modified epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dibasic acids, etc.
• aromatic epoxy resins (C) the reactivity of the secondary hydroxyl group generated by the ring opening of the epoxy group by the reaction with the aromatic dicarboxylic acid (B) with the acryloyl group of the polyfunctional acrylate (A) is high. Since it is high, bisphenol A type epoxy resin is preferable. Moreover, these aromatic epoxy resins (C) can be used alone or in combination of two or more.
• the carboxylic acid (D) is a carboxylic acid having a polymerizable unsaturated group.
• Examples of the carboxylic acid (D) include acrylic acid and methacrylic acid.
• acrylic acid is preferable because of its good curability by active energy ray irradiation.
• These carboxylic acids (D) can be used alone or in combination of two or more.
• the active energy ray-curable composition of the present invention can be produced by the following two steps.
• First step The process with which a polyfunctional acrylate (A), aromatic dicarboxylic acid (B), and an aromatic epoxy resin (C) are made to react.
• Second step The process with which the carboxylic acid (D) which has a polymerizable unsaturated group is made to react with the reaction material obtained at the 1st process.
• the carboxyl group of aromatic dicarboxylic acid (B) and the epoxy group of aromatic epoxy resin (C) couple
• ethylene oxide-modified pentaerythritol triacrylate is used for the polyfunctional acrylate (A)
• isophthalic acid is used for the aromatic dicarboxylic acid (B)
• bisphenol A type epoxy resin is used for the aromatic epoxy resin (C).
• the progress of the reaction in this case is considered to be as shown in the following (Reaction Formula 1).
• the segment which the said aromatic dicarboxylic acid (B) after the Michael addition reaction reacted with the said aromatic epoxy resin (C) is abbreviated.
• n, x, y and z each represent a repeating unit in parentheses.
• the usage-amount of the said aromatic epoxy resin (C) in said 1st process is an epoxy group which the said aromatic epoxy resin (C) has with respect to 1 mol of carboxyl groups which the said aromatic dicarboxylic acid (B) has. Is preferably in the range of 1 to 5, more preferably in the range of 1.1 to 3, and still more preferably in the range of 1.5 to 3.
• the reaction product obtained in the first step has an epoxy group.
• the amount of the polyfunctional acrylate (A) used in the first step is 20 to 20 parts per 100 parts by mass of the total amount of the aromatic dicarboxylic acid (B) and the aromatic epoxy resin (C).
• the range of 300 parts by mass is preferable, the range of 50 to 200 parts by mass is more preferable, and the range of 80 to 120 parts by mass is more preferable.
• the first step is preferably performed in the presence of a catalyst (E).
• a catalyst (E) examples include triphenylphosphine, 2-methylimidazole, trimethylammonium chloride, and the like.
• triphenylphosphine is preferable because the reaction can be easily controlled.
• these catalysts (E) can be used alone or in combination of two or more.
• the first step is preferably carried out in the presence of a polymerization inhibitor (F).
• a polymerization inhibitor (F) a nitroso polymerization inhibitor such as nitrosophenylhydroxylamine ammonium salt; hydroquinone , Quinone polymerization inhibitors such as methoquinone (hydroquinone monomethyl ether) and benzoquinone; radical scavengers such as N, N-diphenylpicrylhydrazyl (DPPH), triphenylmethyl and butylhydroxytoluene; benzotriazole antioxidants Etc.
• methoquinone is preferred because of its high solubility in the resin.
• These polymerization inhibitors (F) can be used alone or in combination of two or more.
• the reaction temperature in the first step is preferably in the range of 100 to 140 ° C., more preferably in the range of 110 to 130 ° C., because the epoxy ring-opening reaction and the addition reaction proceed well.
• the epoxy equivalent of the reaction product obtained in the first step is 100 to 2,000 g / eq. In the range of 100 to 500 g / eq. The range of 100 to 300 g / eq. The range of is more preferable.
• the acid value is preferably in the range of 0.1 to 3.0, more preferably in the range of 0.1 to 2.0, and still more preferably in the range of 0.1 to 1.0.
• the epoxy group of the reaction product obtained in the first step is reacted with the carboxyl group of the carboxylic acid (D) having a polymerizable unsaturated group such as acrylic acid, thereby causing the first step.
• a polymerizable unsaturated group can be introduced into the reaction product obtained in one step.
• the reaction product obtained in the first step is the one shown in (Reaction Formula 1) and acrylic acid is used as the carboxylic acid (D), the following (Reaction Formula 2) )become that way.
• the epoxy equivalent of the active energy ray-curable composition of the present invention obtained through the first step and the second step is 5,000 to 50,000 g / eq. In the range of 10,000 to 50,000 g / eq. The range of 14,000 to 50,000 g / eq. The range of is more preferable.
• the acid value is preferably in the range of 0.5 to 10, more preferably in the range of 0.5 to 5, and further preferably in the range of 0.5 to 3, from the viewpoint of the stability of the composition.
• a polyfunctional acrylate (A ′) may be further added to the active energy ray-curable composition of the present invention. When this polyfunctional acrylate (A ′) is added, it may be added during the second step or after the second step.
• the polyfunctional acrylate (A ′) can be the same as the polyfunctional acrylate (A), and may be the same as or different from the polyfunctional acrylate (A). Ethylene oxide-modified trimethylolpropane triacrylate is preferred.
• These polyfunctional acrylates (A ′) can be used alone or in combination of two or more.
• the active energy ray-curable coating material of the present invention contains the active energy ray-curable composition of the present invention, and other compounds include pigments, dyes, extender pigments, organic or inorganic fillers, active energy rays.
• Additives such as pigment dispersants can be used.
• the active energy ray-curable coating material of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate.
• the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• a cured coating film is formed by irradiating ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator (G) to the active energy ray-curable aqueous coating material of the present invention to improve curability.
• a photosensitizer can be further added to improve curability.
• ionizing radiation such as electron beam, ⁇ -ray, ⁇ -ray, and ⁇ -ray
• it cures quickly without using a photopolymerization initiator or photosensitizer. It is not necessary to add G) or a photosensitizer.
• Examples of the photopolymerization initiator (G) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators.
• Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy.
• examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide.
• Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler ketone and 4,4′-diethylaminobenzophenone; -2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.
• These photopolymerization initiators (G) can be used alone or in combination of two or more.
• the photosensitizer examples include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. And sulfur compounds.
• photopolymerization initiators and photosensitizers are preferably used in an amount of 0.05 to 20 parts by mass, preferably 0.5 to 10 mass% is more preferable.
• the active energy ray-curable coating material of the present invention can be used as a coating material for coating various articles.
• Articles that can be coated with the active energy ray-curable paint of the present invention include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines.
• Equipment casings interior materials for various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; woodwork materials such as furniture; artificial and synthetic leather; FRP bathtubs.
• the application method of the active energy ray-curable paint of the present invention varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, Examples of the method include spin coater, dipping, screen printing, spraying, applicator, and bar coater.
• the active energy ray for curing the active energy ray-curable coating of the present invention is ionizing radiation such as ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, and ⁇ rays.
• curing devices include germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, high-pressure mercury lamps for copying, medium or high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halide lamps, and ultraviolet light that uses natural light as a light source.
• an electron beam by a scanning type or curtain type electron beam accelerator an electron beam by a scanning type or curtain type electron beam accelerator.
• the active energy ray curable printing ink of the present invention contains the active energy ray curable composition of the present invention, and is formulated with other suitable formulations for various printing methods.
• additives such as pigments, dyes, extender pigments, paraffin wax, polyolefin wax, organic solvents, and pigment dispersants can be used.
• a photopolymerization initiator and a photosensitizer are blended as necessary, and the blending amount is the same as in the case of the paint. Furthermore, the same thing can be used also about the active energy ray used in the case of an effect, and the apparatus which irradiates it.
• the active energy ray-curable printing ink of the present invention can be used for printing various printed materials.
• the printed material include paper base materials used for catalogs, pamphlets, cosmetic packages, and the like; films used for various food packaging materials such as polypropylene films and polyethylene terephthalate (PET) films.
• examples of the printing method of the active energy ray-curable printing ink of the present invention include lithographic printing, gravure printing, gravure offset printing, flexographic printing, and the like.
• Example 1 In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 177.5 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (hereinafter abbreviated as “EOTMPTA”), bisphenol A type epoxy resin (Dow “DER331” manufactured by Chemical Japan Co., Ltd., epoxy equivalent of 185 g / eq., Hereinafter abbreviated as “Bis-A type epoxy resin”) 145 parts by mass, terephthalic acid (hereinafter abbreviated as “TPA”) 32 masses Parts, dibutylhydroxytoluene (polymerization inhibitor; hereinafter abbreviated as “BHT”) 1.8 parts by mass, and methoquinone (polymerization inhibitor; hereinafter abbreviated as “MQ”) 0.2 parts by mass.
• ETMPTA ethylene oxide-modified trimethylolpropane triacrylate
• TPP triphenylphosphine
• Example 2 In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 177.5 parts by mass of EOTMPTA, 145 parts by mass of Bis-A type epoxy resin, 32 parts by mass of isophthalic acid (hereinafter abbreviated as “IPA”), After charging 1.8 parts by mass of BHT and 0.2 parts by mass of MQ and raising the temperature to 120 ° C., 2.7 parts by mass of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq.
• EOTMPTA EOTMPTA
• Bis-A type epoxy resin 32 parts by mass of isophthalic acid (hereinafter abbreviated as “IPA”)
• IPA isophthalic acid
• Example 3 In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, EOTMPTA 177.5 parts by mass, Bis-A type epoxy resin 149.5 parts by mass, IPA 21 parts by mass, BHT 1.8 parts by mass, and MQ 0.2 parts by mass Parts were charged and the temperature was raised to 120 ° C., and then 2.7 parts by mass of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq. Then, after charging 28 parts by mass of acrylic acid, 105 parts by mass of EOTMPTA, and 1.2 parts by mass of TPP, the reaction was further carried out at 120 ° C. for 2 hours, so that the epoxy equivalent was 15,500 g / eq. And an active energy ray-curable composition (3) having an acid value of 1.5 was obtained.
• Example 4 In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 177.5 parts by mass of trimethylolpropane triacrylate (hereinafter abbreviated as “TMPTA”), 145 parts by mass of Bis-A type epoxy resin, IPA32 After adding a mass part, 1.8 mass parts of BHT, and 0.2 mass part of MQ, and heating up at 120 degreeC, 2.7 mass parts of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq.
• TMPTA trimethylolpropane triacrylate
• Example 5 In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 177.5 parts by mass of glycerin propoxytriacrylate (hereinafter abbreviated as “GPTA”), 145 parts by mass of Bis-A type epoxy resin, 32 parts by mass of IPA Part, BHT 1.8 parts by mass, and MQ 0.2 parts by mass were heated to 120 ° C., and then 2.7 parts by mass of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq.
• GPTA glycerin propoxytriacrylate
• Example 6 [Preparation of active energy ray curable paint] 100 parts by mass of the active energy ray-curable composition (1) obtained in Example 1 above, 4 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd .; 1-hydroxycyclohexyl-phenylketone), And 20 mass parts of butyl acetate was mixed and the active energy ray-curable coating material (1) was obtained. Subsequently, the following scratch resistance evaluation was performed about the cured coating film of the obtained active energy ray-curable coating material (1).
• a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd .; 1-hydroxycyclohexyl-phenylketone)
• the active energy ray-curable paint (1) obtained above was applied on a glass plate (thickness 2 mm) using an applicator so as to have a dry film thickness of 10 ⁇ m, and after drying the solvent, a high pressure of 80 W / cm. Curing was performed using a mercury lamp at an ultraviolet irradiation amount of 0.8 J / cm 2 to obtain a coating film for evaluation of scratch resistance.
• the obtained coating film for evaluation was obtained with a wear tester (500 g / cm 2 load) in which steel wool (“Bonster No. 0000” manufactured by Nippon Steel Wool Co., Ltd.) was attached to a circular jig having a diameter of 27 mm. The surface was worn 100 reciprocating times.
• the coating film after the test was measured with a haze meter (“NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd.), and the scratch resistance was evaluated according to the following criteria from the obtained haze value.
• ⁇ Haze value is less than 5.
• ⁇ Haze value is 5 or more and less than 10.
• X Haze value is 10 or more.
• Examples 7 to 10 and Comparative Example 2 Instead of the active energy ray-curable composition (1) used in Example 6, the active energy ray-curable compositions (2) to (5) and (R1) obtained in Examples 2 to 5 and Comparative Example 1 were used.
• the active energy ray-curable paints (2) to (5) and (R1) were prepared in the same manner except that (1) was used, and a cured coating film was obtained, and the scratch resistance was evaluated.
• Table 2 summarizes the compositions of the active energy ray-curable paints obtained in Examples 6 to 10 and Comparative Example 2 and the evaluation results of scratch resistance.
• the cured coating films of the active energy ray-curable coatings of Examples 6 to 10 using the active energy ray-curable composition of the present invention have a very low haze value of 1 to 2% after abrasion with steel wool, and are high. It was found to have scratch resistance.
• the active energy ray-curable coating material of Comparative Example 2 is an example using an active energy ray-curable composition that does not use the polyfunctional acrylate (A) and aromatic dicarboxylic acid (B) used in the present invention. It was found that the haze value after abrasion with steel wool was as high as 11% and the scratch resistance was poor.
• Example 11 [Preparation of active energy ray-curable printing ink] 23 parts by mass of the active energy ray-curable composition (1) obtained in Example 1 above, 19 parts by mass of a red pigment (Pigment Red 57-1), 3 parts by mass of a yellow pigment (Pigment Yellow 13), linear 25 parts by mass of polyester acrylate (“Evekril 657” manufactured by USB Chemicals; hereinafter abbreviated as “PEsA”), 13 parts by mass of TMPTA, 8 parts by mass of talc, 5 parts by mass of polyethylene wax, photopolymerization initiator (BASF Japan Ltd.) “Irgacure 907”, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one; hereinafter abbreviated as “photopolymerization initiator (1)”) 2 parts by mass, photopolymerization initiator (4,4′-diethylaminobenzophenone; hereinafter abbreviated as “photopolymerization initiator (2)”) 2
• the active energy ray-curable printing ink (1) obtained above was applied to a polyethylene terephthalate film (corona-treated PET film manufactured by Toyobo Co., Ltd .; thickness 50 ⁇ m) as a base material using a bar coater # 4.
• the film was cured with an ultraviolet irradiation amount of 0.8 J / cm 2 using an 80 W / cm high-pressure mercury lamp to obtain a coating film for evaluating adhesion.
• a cellophane tape was applied to the surface of the obtained coating film for evaluation, and the peeled state of the coating film from the substrate when peeled vigorously was visually observed, and the adhesion was evaluated according to the following criteria.
• Example 12 to 15 and Comparative Example 3 Instead of the active energy ray-curable composition (1) used in Example 11, the active energy ray-curable compositions (2) to (5) and (R1) obtained in Examples 2 to 5 and Comparative Example 1 were used.
• the active energy ray-curable printing inks (2) to (5) and (R1) were prepared in the same manner except that was used. Using the obtained active energy ray-curable printing ink, evaluation of misting resistance, adhesion and solvent resistance was carried out in the same manner as in Example 11.
• Table 3 summarizes the compositions of the active energy ray-curable printing inks obtained in Examples 11 to 15 and Comparative Examples 3 and 4, and the evaluation results of misting resistance, adhesion, and solvent resistance.
• the active energy ray-curable printing inks of Examples 11 to 15 using the active energy ray-curable composition of the present invention were excellent in misting resistance. Moreover, it turned out that the cured coating film of the active energy ray curable printing ink of this invention has very high adhesiveness with respect to a polyethylene terephthalate film, and has high solvent resistance.
• the active energy ray-curable printing ink of Comparative Example 3 is an example using an active energy ray-curable composition that did not use the polyfunctional acrylate (A) and aromatic dicarboxylic acid (B) used in the present invention.
• this active energy ray-curable printing ink has a very large amount of mist and has a problem in misting resistance.
• the cured coating film of this printing ink is poor in adhesiveness with respect to a polyethylene terephthalate film, and also solvent resistance is not enough.
• the active energy ray-curable printing ink of Comparative Example 4 is an example in which an active energy ray-curable composition not using the polyfunctional acrylate (A) and aromatic dicarboxylic acid (B) used in the present invention and a rosin resin are used in combination.
• this active energy ray-curable printing ink can suppress the amount of mist as compared with that of Comparative Example 3, but the cured coating film of this printing ink has poor adhesion to the polyethylene terephthalate film. It was found that there was no solvent resistance.

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• Inks, Pencil-Leads, Or Crayons (AREA)
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• 2013
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