Active energy ray-curable composition and laminate using the same

Abstract

To provide an active energy ray-curable composition which exhibits superior printing suitability (viscosity stability), and which forms a cured layer having superior adhesion to a substrate and a printed layer, friction resistance, and moist-heat resistance when printed and cured.SOLUTION: An active energy ray-curable composition comprises a polyfunctional urethane (meth)acrylate, a monofunctional ethylenically unsaturated monomer, and resin fine particles, where the polyfunctional urethane (meth)acrylate has a weight-average molecular weight of 3000 to 20000, and solids in the active energy ray-curable composition have a hydroxyl value of 30 mgKOH / g or less.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, in the field of packages using a paper substrate (also referred to as paper containers), for the purpose of imparting durability and cosmetic properties to printed matter, various substrates are printed with color ink and then coated with coating varnish. Regarding paper container packages, when displayed in stores after printing, there are cases where glossiness and matte finish (matte property) are required for cosmetic purposes. In particular, in recent years, the demand for printed matter with a matte effect has been increasing.

[0003] Conventionally, generally, for matte coating varnishes for paper container packages, solvent-based matte coating varnishes containing a resin, a matting agent, and a solvent have been used for the purpose of imparting a high-class feeling by high matte property. Generally, in the drying process after printing, the volume of the varnish film decreases as the solvent component volatilizes from the varnish film, and as a result, a high matting agent is oriented on the surface of the varnish film, and a high matting effect can be obtained. However, it is inferior in workability and environmental friendliness. Furthermore, in solvent-based matte coating varnishes, since the solid content of the ink fluctuates due to the volatilization of the solvent component during printing, there are concerns about viscosity fluctuations during printing and the risk of environmental pollution by the volatilized solvent.

[0004] Therefore, in recent years, solvent-free activated energy ray matte coating varnishes with improved workability and environmental friendliness have been developed. For example, Patent Document 1 discloses an active energy ray curable coating varnish containing a photopolymerizable acrylate monomer, resin beads, and a photoinitiator, wherein the resin beads are composed of two types of resin beads with different average particle diameters, and the active energy ray curable coating varnish is characterized by a printed matter excellent in matte feeling and abrasion resistance has been proposed.

[0005] In addition, Patent Document 2 discloses a solvent-free active energy ray-curable composition containing an active energy ray-curable compound, an inorganic matting agent, and an aluminum chelate compound, wherein the inorganic matting agent is silica having an average particle diameter of 1 to 15 μm, a thixotropic coefficient at 25°C of 2 or less, and a viscosity at the coating environment temperature of 1000 mPa·s or less. A solvent-free active energy ray-curable composition has been proposed.

[0006] In addition, Patent Document 3 discloses an active energy ray-curable resin composition comprising a urethane (meth)acrylate compound obtained by reacting a polyol compound, a hydroxyl group-containing (meth)acrylate compound, and a polyvalent isocyanate compound, and an organic filler, wherein the polyol compound contains a polyol compound having a weight average molecular weight of 60 to 300 and a polyol compound having a weight average molecular weight of 3,000 to 20,000, and as the organic filler, a polyurethane filler and a polyethylene filler are used in combination. An active energy ray-curable resin composition has been proposed.

[0007] In addition, Patent Document 4 discloses an active energy ray-curable composition containing a polyfunctional urethane (meth)acrylate, a monofunctional ethylenically unsaturated monomer, and resin fine particles, wherein the weight average molecular weight of the polyfunctional urethane (meth)acrylate is 1000 to 7000, and it does not contain an organic solvent or contains 5% by mass or less in the total mass of the composition, the viscosity of the composition at 25°C is 250 to 2500 mPa·s, and the monofunctional ethylenically unsaturated monomer contains a hydroxyalkyl (meth)acrylate. An active energy ray-curable composition has been proposed.

[0008] However, the technologies disclosed in Patent Documents 1 and 2 above are solvent-free and excellent in workability and environmental properties, but they do not have sufficient matting properties compared to the conventionally mainstream solvent-based mat coating varnishes, and there are still problems for use in paper packaging applications that require high matting properties in recent years.

[0009] On the other hand, while Patent Document 3 is considered to have sufficient matting from the viewpoint of cosmetic properties, it is a composition containing a solvent to impart coatability, and there are still problems in workability and environmental properties.

[0010] On the other hand, Patent Document 4 is solvent-free and excellent in workability, environmental properties, and cosmetic properties, and further improvement in adhesion to a substrate and a printed layer and abrasion resistance is expected in this field.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0012] An object of the present invention is to provide an active energy ray curable composition for forming a cured layer, which is excellent in printing suitability (viscosity stability), and has excellent adhesion to a substrate and a printed layer, abrasion resistance, and wet heat resistance when printed and cured.

Means for Solving the Problems

[0013] As a result of intensive studies on the above problems, the inventors have found that the problems can be solved by using the active energy ray curable composition described below, and have completed the present invention.

[0014] That is, the present invention is an active energy ray curable composition containing a polyfunctional urethane (meth) acrylate, a monofunctional ethylenically unsaturated monomer, and resin fine particles, The weight average molecular weight of the polyfunctional urethane (meth)acrylate is from 3,000 to 20,000, and the hydroxyl value of the solid content of the active energy ray curable composition is 30 mgKOH / g or less, relating to an active energy ray curable composition.

[0015] In addition, the present invention relates to the active energy ray curable composition in which the monofunctional ethylenically unsaturated monomer has a heterocyclic structure.

[0016] In addition, the present invention further relates to the active energy ray curable composition containing a photopolymerization initiator.

[0017] In addition, the present invention relates to the active energy ray curable composition in which the polyfunctional urethane (meth)acrylate has a structural unit derived from polyether.

[0018] In addition, the present invention relates to the active energy ray curable composition in which the resin fine particles are urethane resin fine particles.

[0019] In addition, the present invention further relates to the active energy ray curable composition containing a silicon acrylate.

[0020] In addition, the present invention relates to the active energy ray curable composition for use on a paper substrate.

[0021] In addition, the present invention relates to a laminate having a printed layer and a cured layer formed from the active energy ray curable composition on a paper substrate.

[0022] In addition, the present invention relates to a method for producing a laminate in which the active energy ray curable composition is applied and cured on a substrate by any one of flexographic printing, screen printing, and roll coater methods.

Advantages of the Invention

[0023] The present invention makes it possible to provide an active energy ray curable composition for forming a cured layer, which is excellent in printing suitability (viscosity stability), and when printed and cured, is excellent in adhesion to a substrate and a printed layer, abrasion resistance, and moisture and heat resistance.

Embodiments for Carrying Out the Invention

[0024] Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof.

[0025] In this specification, the "solid content of the active energy ray curable composition" means the total mass of the components obtained by removing water and organic solvents from the active energy ray curable composition. Polyfunctional urethane (meth)acrylate, monofunctional ethylenically unsaturated monomer, resin fine particles, etc. are included in the "solid content".

[0026] In the following description, (meth)acrylic and (meth)acrylate mean methacrylic and acrylic, methacrylate and acrylate, respectively. Also, (meth)acryloyl means methacryloyl and acryloyl. Note that polyfunctional urethane acrylate is synonymous with polyfunctional urethane (meth)acrylate. In addition, the active energy ray curable composition may sometimes be simply referred to as the "composition", which is synonymous.

[0027] The present invention relates to an active energy ray curable composition containing polyfunctional urethane (meth)acrylate, a monofunctional ethylenically unsaturated monomer, and resin fine particles, wherein the weight average molecular weight of the polyfunctional urethane (meth)acrylate is 3000 to 20000, and the hydroxyl value of the solid content of the composition is 30 mgKOH / g or less. Preferably, the composition does not contain an organic solvent or contains 5% by mass or less in the total mass of the composition. By setting the weight-average molecular weight of the polyfunctional urethane acrylate within the corresponding range and the hydroxyl value of the composition to 30 mgKOH / g or less, the cohesive force within the composition is relaxed, the intermolecular interaction with the substrate and the printing layer is improved, and the adhesion, abrasion resistance, and moisture and heat resistance become good. By setting the organic solvent in the total mass of the composition to 5% by mass or less, the viscosity stability becomes good, and it is considered that the printing suitability, the film physical properties of the printed matter, etc. are improved. Note that the above shows the effects based on chemical considerations, and the present invention is not limited only to the aspects showing these effects.

[0028] (Hydroxyl value) In the present invention, the hydroxyl value means the amount of hydroxyl groups in 1 g of the composition calculated by esterifying or acetylating the hydroxyl groups in the composition and back-titrating the remaining acid with an alkali, converted to the number of mg of potassium hydroxide, and is the measured value performed according to JIS K0070. In order to make the hydroxyl value of the solid content of the composition 30 mgKOH / g or less, it is a preferred embodiment to use a polyfunctional urethane (meth) acrylate and a monofunctional ethylenically unsaturated monomer having a hydroxyl value of 30 mgKOH / g or less. It is preferable that the hydroxyl value of the monofunctional ethylenically unsaturated monomer is 30 mgKOH / g or less, preferably 20 mgKOH / g or less, and more preferably 10 mgKOH / g or less. By being within the above range, the moisture and heat resistance becomes good. It is preferable that the hydroxyl value of the solid content of the composition is 20 mgKOH / g or less, more preferably 10 mgKOH / g or less, and particularly preferably 5 mgKOH / g or less. Note that the hydroxyl value of 30 mgKOH / g or less includes the case of 0 KOH / g or less. By the hydroxyl value being within the above preferred range, the moisture and heat resistance becomes good.

[0029] (Polyfunctional urethane acrylate) The weight average molecular weight of the polyfunctional urethane acrylate used in the present invention is from 3,000 to 20,000. When the weight average molecular weight is within the above range, the viscosity of the composition can be appropriately maintained to improve the coating suitability, and excessive penetration into the paper substrate can be avoided. Moreover, the cured layer formed from the ultraviolet curable resin composition becomes uniform. Furthermore, the cured layer maintains an appropriate hardness and does not crack. Also, due to its polyfunctionality, it has good blocking resistance. The weight average molecular weight is preferably from 3,500 to 15,000, and still more preferably from 4,000 to 10,000. Also, the number of functional groups of the polyfunctional urethane acrylate is preferably 2 to 3, and still more preferably 2. Here, the number of functional groups refers to polymerizable (meth)acrylate groups and other unsaturated double bond groups. When the number of functional groups is within the above range, the adhesion of the cured layer is improved.

[0030] Note that the above weight average molecular weight refers to the measured value by gel permeation chromatography. For example, it can be measured using GPC (gel permeation chromatography) "Shodex GPC System - 21" manufactured by Showa Denko K.K. GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent according to the difference in their molecular sizes. As the solvent, tetrahydrofuran is used, and it is preferable to convert the weight average molecular weight in terms of polystyrene.

[0031] The glass transition temperature (Tg) of the polyfunctional urethane acrylate is preferably from -50 to 35°C, still more preferably from -45 to 30°C, and even more preferably from -40 to 25°C. When within the above range, the adhesion and ruled line cracking resistance of the cured layer are improved. Note that the glass transition temperature represents the measured value by a differential scanning calorimeter (DSC), and the midpoint between the endothermic start temperature and the end temperature based on the glass transition in the DSC curve is defined as the glass transition temperature.

[0032] The active energy ray curable composition preferably contains 5 to 40% by mass of the polyfunctional urethane acrylate, and more preferably 10 to 30% by mass. When within the above range, the abrasion resistance is improved.

[0033] The following embodiments of the polyfunctional urethane acrylate are preferred. For example, an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under conditions of an excess of isocyanate groups is reacted with a (meth)acrylate having a hydroxyl group, or one obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under conditions of an excess of hydroxyl groups can be reacted with (meth)acrylates having isocyanate groups.

[0034] The above polyol, hydroxyl group-containing (meth)acrylate, and polyisocyanate constituting the polyfunctional urethane acrylate will be described.

[0035] <Polyol> As the above polyol constituting the polyfunctional urethane acrylate, known ones can be used, and polyether polyols, polyester polyols, polyolefin polyols (polybutadiene polyols, polyisoprene polyols), polycarbonate polyols, polysiloxane polyols, (meth)acrylic polyols, etc. are preferably mentioned, and they may have an aliphatic structure or an alicyclic structure. Among these, polyether polyols are preferred. When using polyether polyols, the polyfunctional urethane acrylate will have a structural unit derived from polyether, and the adhesion will be improved. The polyfunctional urethane acrylate preferably contains 20 to 99% by mass of the structural unit derived from polyether, and more preferably 40 to 98% by mass. Furthermore, as the above polyether polyol, polyethylene glycol is still more preferably used. By using polyethylene glycol, the polyfunctional urethane (meth)acrylate will have a structural unit derived from polyethylene glycol, and the adhesion can be further improved.

[0036] <Polyisocyanate> As the above-mentioned polyisocyanate constituting the polyfunctional urethane acrylate, known ones can be used, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Examples of the aromatic diisocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate-benzyl chloride. Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimer diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and dimer diisocyanate obtained by converting the carboxy group of dimer acid into an isocyanate group. These may form trimers to have an isocyanurate ring structure. These polyisocyanates can be used alone or in combination of two or more. Among them, preferably, they are tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and an isocyanurate form of hexamethylene diisocyanate.

[0037] <(Meth)acrylate having a hydroxyl group> Specific examples of the “(meth)acrylate having a hydroxyl group” that constitutes the polyfunctional urethane acrylate include trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl-α-(hydroxymethyl) (meth)acrylate, monofunctional glycerol (meth)acrylate, or (meth)acrylate esters having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone, and alkylene oxide-added (meth)acrylate esters such as those obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to the above hydroxyl group-containing (meth)acrylate. Among these, those containing at least one selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred.

[0038] <Mono-functional ethylenically unsaturated monomer> Examples of the monofunctional ethylenically unsaturated monomer used in the present invention include (alkyl)(meth)acrylates having 1 to 18 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and further alkylphenols such as benzyl (meth)acrylate, butylphenol, octylphenol, nonylphenol or dodecylphenol, (meth)acrylates of ethylene oxide adducts, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecane monomethylol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, β-carboxyethyl (meth)acrylate, (meth)acrylic acid dimer, ω-carboxy-polycaprolactone mono(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-vinylformamide, (meth)acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclic trimethylolpropane formal acrylate, 3-ethyl-3 oxetanyl-methyl (meth)acrylate, (2-methyl-2-ethyl-1,Examples thereof include (3 - dioxolan - 4 - yl) methyl acrylate and the like.,

[0039] Among them, it is preferable to contain monofunctional ethylenically unsaturated monomers having a heterocyclic structure such as N - vinylpyrrolidone, acryloylmorpholine, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl alcohol polyacrylate ester, cyclic trimethylolpropane formal acrylate, 3 - ethyl - 3 - oxetanyl - methyl (meth) acrylate, (2 - methyl - 2 - ethyl - 1,3 - dioxolan - 4 - yl) methyl acrylate. By containing a heterocyclic structure, the viscosity of the composition can be appropriately maintained and the moisture and heat resistance is improved. The heterocyclic ring preferably contains a nitrogen atom or an oxygen element, and more preferably contains an oxygen atom. Further, the heterocyclic ring preferably contains a 4 - to 6 - membered ring structure, and still more preferably a 5 - membered ring structure. A tetrahydrofuran ring structure is even more preferable. By containing a tetrahydro ring, the viscosity stability of the composition and the adhesion of the cured layer are improved., The content of the monofunctional ethylenically unsaturated monomer having a heterocyclic structure in the total mass of the monofunctional ethylenically unsaturated monomers is preferably 60 - 100% by mass, more preferably 70 - 100% by mass, still more preferably 80 - 100% by mass, and particularly preferably 85 - 100% by mass.,

[0040] The monofunctional ethylenically unsaturated monomer has the effect of significantly reducing the viscosity of the active energy ray - curable composition, improving the smoothness of the coating film, and further improving the abrasion resistance. From the above viewpoints, the content of the monofunctional ethylenically unsaturated monomer in the total mass of the active energy ray - curable composition is preferably 30 - 60% by mass, still preferably 35 - 55% by mass, and still more preferably 40 - 50% by mass. Also, the mass ratio of the polyfunctional urethane acrylate to the monofunctional ethylenically unsaturated monomer is preferably 10:90 - 50:50, preferably 20:80 - 40:60, and still more preferably 25:75 - 35:65.,

[0041] <Bifunctional ethylenically unsaturated monomer> The composition of the present invention preferably also contains a bifunctional ethylenically unsaturated monomer. Examples of the bifunctional ethylenically unsaturated monomer include polyethylene glycol 200 diacrylate, polyethylene glycol 300 diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polyethylene glycol 1000 diacrylate, tetraethylene glycol diacrylate, etc., and those containing an ether structure are preferred. The bifunctional ethylenically unsaturated monomer is preferably contained in an amount of 0 to 15% by mass, more preferably 0 to 7% by mass, based on the total mass of the composition. Note that the bifunctional ethylenically unsaturated monomer does not include the case where it is the above-mentioned polyfunctional urethane acrylate.

[0042] <Resin fine particles> In the present invention, the resin fine particles are responsible for the functions of abrasion resistance, matting property, and antiblocking property. The average particle diameter of the resin fine particles is preferably 1 to 10 μm, more preferably 1.5 to 8 μm, still more preferably 2 to 6 μm, and particularly preferably 2 to 3 μm. The average particle diameter referred to here means the volume average particle diameter measured by the laser diffraction method, and can be measured using, for example, T330EXII manufactured by Microtrac Bell Co., Ltd. The resin fine particles are preferably contained in an amount of 10 to 40% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass, based on the total mass of the active energy ray-curable composition.

[0043] Preferable specific examples of the resin fine particles include, for example, urethane resin fine particles, silicone resin fine particles, melamine resin fine particles, melamine-benzoguanamine resin fine particles, acrylic resin fine particles (e.g., polymethyl methacrylate resin fine particles), acrylic-styrene copolymer resin fine particles, polycarbonate resin fine particles, polyethylene resin fine particles, polystyrene resin fine particles, benzoguanamine resin fine particles, and the like. These may be used alone or in combination of two or more. Among them, urethane resin fine particles are more preferable. The above resin fine particles may be used in combination of two or more as needed.

[0044] Specific examples of the urethane resin fine particles include, for example, crosslinked urethane beads such as Art Pearl C-1000 transparent, Art Pearl C-600 transparent, Art Pearl C-400 transparent, Art Pearl C-800, Art Pearl MM-120T, Art Pearl JB-800T, Art Pearl JB-600T, Art Pearl P-800T, Art Pearl P-400T (manufactured by Negami Kogyo Co., Ltd.).

[0045] Specific examples of the silicone resin fine particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), Treffil E-506S, EP-9215 (manufactured by Toray Dow Corning Co., Ltd.), and the like.

[0046] Specific examples of the melamine resin fine particles include Epotar SS, Epotar S, Epotar FS, Epotar S6, Epotar S12 (manufactured by Nippon Shokubai Co., Ltd.), and the like. Specific examples of the melamine-benzoguanamine resin fine particles include Epotar M30 (manufactured by Nippon Shokubai Co., Ltd.).

[0047] Specific examples of the acrylic resin fine particles include Epotar MA1002, Epotar MA1004, Epotar MA1006, Epotar MA1010 (manufactured by Nippon Shokubai Co., Ltd.), Toughic FH-S005, Toughic FH-S008, Toughic FH-S010, Toughic FH-S015, Toughic FH-S020 (manufactured by Toyobo Co., Ltd.), Chemisnow M Examples thereof include X-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, MX-3000 (manufactured by Soken Chemical & Engineering Co., Ltd.).

[0048] Specific examples of the acrylic-styrene copolymer resin fine particles include Epotar MA2003 (manufactured by Nippon Shokubai Co., Ltd.), FS-102, FS-201, FS-301, MG-451, MG-351 (manufactured by Nippon Paint Industrial Coatings Co., Ltd.).

[0049] Specific examples of the polycarbonate resin fine particles include the fine particles described in JP-A-2014-125495, the fine particles obtained by the production method described in JP-A-2011-26471, the fine particles obtained by the method described in JP-A-2001-213970, and the like.

[0050] Specific examples of the polyethylene resin fine particles include Mipelon XM-220, XM221U (manufactured by Mitsui Chemicals, Inc.), Flow Beads LE-1080 (manufactured by Sumitomo Seika Chemicals Co., Ltd.).

[0051] Specific examples of the polystyrene-based fine particles include Chemisnow SX-130H, SX-350H, SX-500H (manufactured by Soken Chemical & Engineering Co., Ltd.).

[0052] Specific examples of the benzoguanamine resin fine particles include Epotar MS, Epotar M05, Epotar L15 (manufactured by Nippon Shokubai Co., Ltd.).

[0053] <Photoinitiator> The active energy ray-curable composition of the present invention also contains a photopolymerization initiator. The photopolymerization initiator generates radicals by active energy such as light irradiation or heating, and initiates the crosslinking reaction and polymerization reaction of the acrylate groups of the polyfunctional urethane acrylate and the monofunctional ethylenically unsaturated monomer. Preferred examples of the photopolymerization initiator include acetophenone-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and the like. Among them, acetophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and the like are preferable. The photopolymerization initiator is preferably contained in an amount of 1 to 10% by mass, more preferably 2 to 7% by mass, and still more preferably 3 to 5% by mass in the total mass of the composition.

[0054] Examples of the acetophenone-based photopolymerization initiator include acetophenone-based photopolymerization initiators such as 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone.

[0055] Examples of alkylphenone-based photoinitiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and the like.

[0056] Examples of benzoin-based photoinitiators include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

[0057] Examples of benzophenone-based photoinitiators (d-1) include benzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, methyl-o-benzoylbenzoate, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3-dimethyl-4-methoxybenzophenone, and the like. Among them, 4-methylbenzophenone is preferred.

[0058] Examples of thioxanthone-based photoinitiators include thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

[0059] Examples of anthraquinone-based photoinitiators include α-acyloxime ester, benzyl, methylbenzoyl formate ("Biocure 55"), 2-ethylanthraquinone, and the like.

[0060] Examples of acylphosphine oxide-based photoinitiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Omnirad TPO"), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Omnirad 819"), and the like.

[0061] As the photoinitiator, one or more thereof may be used in combination.

[0062] <Organic solvent in the composition> In order to solve the problems of the present invention, it is more effective that the amount of the organic solvent in the composition is either not containing the organic solvent or 5% by mass or less. This is because the printability is improved and the film physical properties of the printed matter are improved within this range.

[0063] <Viscosity of the composition> The viscosity of the composition is preferably 250 to 2500 mPa·s at 25°C, more preferably 500 to 2000 mPa·s. When it is within this range, it has a high effect of suppressing excessive penetration into paper substrates and the like after coating by printing or the like. In addition, the surface of the cured layer becomes a uniform film, and there is an advantage that stains and the like are less likely to occur. Here, the viscosity mentioned is an assumed value by the method described in JIS K5600-2. For example, it can be measured at a shear rate of 100 per second in a 25°C environment using a cone plate viscometer with a cone having a cone diameter of 35 mm and a cone angle of 2°.

[0064] <Additives> The active energy ray-curable composition of the present invention can appropriately contain known additives. For example, leveling agents, polymerization inhibitors, ultraviolet absorbers, light stabilizers, sensitizers, curing agents, plasticizers, wetting agents, adhesion aids, defoaming agents, antistatic agents, etc. can be used, and there are no particular restrictions.

[0065] <Leveling agent> The active energy ray-curable composition of the present invention preferably contains a leveling agent. The leveling agent is preferably contained in an amount of 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 3 to 7% by mass in the total mass of the active energy ray-curable composition. Further, as the leveling agent, it is preferable to use a silicone acrylate. By using a silicone acrylate, the abrasion resistance becomes good.

[0066] <Silicone acrylate> Specific examples of the silicone acrylate include TEGO Rad 2100, TEGO Rad 2200 N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, TEGO Rad 2550, TEGO Rad 2650, TEGO Rad 2700, TEGO Rad 2800 (manufactured by Evonik), BYK-UV 3500, BYK-UV 3505, BYK-UV 3530, BYK-UV 3570, BYK-UV 3575, BYK-UV 3576 (manufactured by BYK), etc.

[0067] <Production of active energy ray-curable composition> As a method for producing the active energy ray-curable composition, a polyfunctional urethane acrylate having a weight average molecular weight of 3000 to 20000, a monofunctional ethylenically unsaturated monomer, resin fine particles, and a photopolymerization initiator are stirred with a stirrer with blades (disper) or the like for about 30 minutes to 3 hours. In addition, when it is difficult to mix and the viscosity and the like are likely to become non-uniform, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, or the like may be used.

[0068] When the active energy ray-curable composition of the present invention contains bubbles, unexpectedly large particles, etc., it is preferable to remove them by filtration or the like in order to reduce the print quality. A conventionally known filter can be used.

[0069] <Production of laminate> The manufacturing method of the laminate of the present invention is not particularly limited, but preferably, it is formed by coating and curing an active energy ray-curable composition on a paper substrate or a film substrate. Note that a printing layer made of a printing ink composition may be formed on the substrate, and further, the active energy ray-curable composition of the present invention may be printed and cured on the printing layer to form a laminate. The cured layer formed from the active energy ray-curable composition preferably has a thickness of 1 to 30 μm, more preferably 1 to 20 μm, still more preferably 1 to 10 μm, and particularly preferably 1 to 5 μm.

[0070] The coating method of the active energy ray-curable composition is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, flow coating, gravure printing, flexographic printing, roll coater, spin, dispenser, inkjet printing, screen printing, etc. Among them, flexographic printing, screen printing, and roll coater are preferred.

[0071] Examples of the ultraviolet rays for curing the active energy ray-curable composition include far ultraviolet rays, ultraviolet rays, and near ultraviolet rays. On the other hand, it is also possible to use electron beams or proton beams. In this case, curing can be achieved without using a photoinitiator, but curing by ultraviolet irradiation is preferred in terms of curing speed, availability of irradiation devices, price, etc.

[0072] As a method of curing by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc. that emit light in the wavelength range of 150 to 450 nm are used, and the integrated light amount is 30 to 5000 mJ / cm 2 、preferably 100 to 1000 mJ / cm 2 and irradiation may be performed. After ultraviolet irradiation, heating may be performed as necessary to complete the curing.

[0073] When applying the active energy ray-curable composition, the film thickness (film thickness after curing) is preferably usually 1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. Within this range, there is no curing inhibition, the ultraviolet irradiation time can be shortened, and the productivity is good.

[0074] <Paper substrate> In the present invention, the substrate is preferably a paper substrate. The paper substrate is preferably ordinary paper, cardboard, etc. There is no particular specification for the film thickness, but those with a thickness of 0.2 mm to 1.0 mm can be preferably used, and the printing surface may be corona-treated. Also, the paper substrate may be vapor-deposited with a metal such as aluminum on the surface for the purpose of imparting design properties, and may further be surface-coated with an acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resin, and may further be surface-treated such as corona treatment. For example, coated cardboard paper, Mary-coated paper, etc. are preferably mentioned.

[0075] <Film substrate> The film substrate used in the present invention is preferably ordinary PET (polyethylene terephthalate), PVC (polyvinyl chloride), etc., and there is no particular limitation. As for the film thickness, those with a thickness of 0.02 mm to 1.0 mm can be preferably used, and the substrate surface may be corona-treated. Also, the film substrate may be surface-coated with an acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resin, and may further be surface-treated such as corona treatment. For example, Cosmo Shine A4300 (manufactured by Toyobo), E5101 (manufactured by Toyobo), and Crisper K2323 (manufactured by Toyobo), etc. can be mentioned.

[0076] <Printing ink composition> The above printing ink composition may be, for example, a known gravure ink composition, flexographic ink composition, ultraviolet curable flexographic ink composition, offset ink composition, ultraviolet curable offset ink composition, or other ink composition, and any printing ink composition may be used. Among them, when using an ultraviolet curable offset ink composition or an ultraviolet curable flexographic ink composition, if an active energy ray curable composition is laminated, the curing reaction by ultraviolet rays or the like occurs between the layers, improving the adhesion. Therefore, as the printing ink composition, an ultraviolet curable offset ink composition and an ultraviolet curable flexographic ink composition are more preferable.

[0077] <Printing of Printing Ink> As a printing method of the printing ink composition, a known method can be used. For example, a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, etc. can be mentioned. As the thickness of the ink layer, 0.1 to 15 μm is preferable. It is still more preferable to be 0.5 to 12 μm. The printing ink composition may be an organic solvent type or an aqueous type, and may further be any of ultraviolet curable ink compositions. Also, the above printing ink compositions may be combined to form an ink layer, and after printing, it can be dried or cured by ultraviolet rays to form a printing layer.

Examples

[0078] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the present invention, parts and % represent parts by mass and mass % unless otherwise noted.

[0079] <Hydroxyl Value> Measured according to the method described in JIS K0070. <Weight Average Molecular Weight> The weight average molecular weight was determined as the converted molecular weight using polystyrene as a standard substance by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation). The measurement conditions are shown below. Column: The following columns were connected in series and used. TSKgel Super AW 2500 manufactured by Tosoh Corporation TSKgel Super AW 3000 manufactured by Tosoh Corporation TSKgel Super AW 4000 manufactured by Tosoh Corporation TSKgel guard column Super AW H manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Measurement Conditions: Column Temperature 40°C Eluent: Tetrahydrofuran Flow Rate: 1.0 mL / min

[0080] <Glass Transition Temperature> The glass transition temperature (Tg) was determined by DSC (Differential Scanning Calorimetry). The measuring instrument used was DSC 8231 manufactured by Rigaku Corporation. The measurement temperature range was -70 to 150°C, the heating rate was 10°C / min, and the midpoint between the start temperature and the end temperature of the endotherm based on the glass transition in the DSC curve was taken as the glass transition temperature.

[0081] <Synthesis Example of Urethane Acrylate (UA1)> While introducing nitrogen gas into a reactor equipped with a thermometer, a stirrer, a reflux condenser, a stirring device, and a nitrogen gas inlet tube, 1001 parts (4 mol) of diphenylmethane diisocyanate, 1000 parts (1 mol) of polyethylene glycol with a number average molecular weight of 1000, and 4000 parts (2 mol) of polyethylene glycol with a number average molecular weight of 2000 were mixed and reacted at 80°C for 4 hours while stirring to obtain a terminal isocyanate prepolymer. Next, 232 parts (2 mol) of 2-hydroxyethyl acrylate and 1.247 parts (500 ppm) of p-methoxyphenol were charged into the obtained terminal isocyanate prepolymer, and the mixture was stirred while blowing air and reacted at 80°C for 4 hours. After confirming the disappearance of the peak attributed to the isocyanate group by IR spectrum and terminating the reaction, the mixture was cooled to 40°C to obtain a pale yellow liquid (UA1). The weight average molecular weight of urethane acrylate UA1 was 5100, the Tg was -30°C, and the number of functional groups was 2.

[0082] Urethane acrylates (UA2 to UA11) were synthesized in the same manner as in the above synthesis example, except that the raw material compounds shown in Table 1 were used. The abbreviations of the raw material compounds in Table 1 are shown below.

[0083] MDI: Diphenylmethane diisocyanate IPDI: Isophorone diisocyanate Sumidur N3390: Hexamethylene diisocyanate trimer (manufactured by Sumitomo Bayer Urethane Co., Ltd.) PEG1000: Polyethylene glycol with a number average molecular weight of 1000 (polyether polyol) PEG2000: Polyethylene glycol with a number average molecular weight of 2000 (polyether polyol) PEG6000: Polyethylene glycol with a number average molecular weight of 6000 (polyether polyol) PTG2000: Polytetramethylene glycol with a number average molecular weight of 2000 (polyether polyol) PMPA2000: Poly(3-methyl-1,5-pentane adipate) diol with a number average molecular weight of 2000 NISSO-PB G-1000: Polydiene with hydroxyl groups at both ends and a number average molecular weight of 1400 (manufactured by Nippon Soda Co., Ltd.) 2HEA: 2-Hydroxyethyl acrylate

[0084]

Table 1

[0085] (Example 1: Preparation of active energy ray curable composition S1) 19 parts of urethane acrylate UA1, 47 parts of THFA (tetrahydrofurfuryl acrylate), 25 parts of ARTPEARL MM-120T (urethane-based fine particles, average particle diameter 2 μm, glass transition temperature "Tg" 22 °C, manufactured by Negami Kogyo Co., Ltd.), 3 parts of Omnirad184 (1-hydroxycyclohexyl phenyl ketone, manufactured by IGM), 1 part of Omnirad819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by IGM), and 5 parts of silicone acrylate (TEGO Rad 2100, manufactured by Evonik) as a leveling agent were mixed and stirred with a blade stirrer for 90 minutes to obtain an active energy ray-curable composition S1. Regarding the abbreviations of the raw materials in Table 2, they are shown below.

[0086] <Monofunctional ethylenically unsaturated monomer> ·4HBA: 4-Hydroxybutyl acrylate ·ACMO: Acryloylmorpholine ·CTFA: Cyclic trimethylolpropane formal acrylate <Bifunctional ethylenically unsaturated monomer> ·TEGDA: Tetraethylenediacrylate <Resin fine particles> ·ARTPEARL C-800 transparent: Urethane resin fine particles, average particle diameter 6 μm, Tg = -13 °C, manufactured by Negami Kogyo Co., Ltd. ·ARTPEARL C-1000 transparent: Urethane resin fine particles, average particle diameter 3 μm, Tg = -13 °C, manufactured by Negami Kogyo Co., Ltd. ·ARTPEARL J-4P: Acrylic resin fine particles, average particle diameter 2.2 μm, manufactured by Negami Kogyo Co., Ltd. ·Silosphere C-1504: Spherical silica, average particle diameter 4.5 μm, manufactured by Fuji Silysia Chemical Ltd. <Photoinitiator> ·OmniradTPO: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, manufactured by IGM ·Omnirad1173: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, manufactured by IGM <Additive> · Silicon type leveling agent: TEGO Glide 420, manufactured by Evonik · Non-silicon leveling agent: BYK 350, manufactured by BYK <Organic solvent> · PGM-AC: Propylene glycol monomethyl ether acetate

[0087] (Examples 2 - 28: Preparation of active energy ray curable compositions S2 - S28) Active energy ray curable compositions S2 - S28 were obtained in the same manner as in Example 1, except that the raw materials shown in Table 2 - 1 were used at the described compounding ratios.

[0088] (Comparative Examples 1 - 5: Preparation of active energy ray curable compositions T1 - T5) Active energy ray curable compositions T1 - T5 were obtained in the same manner as in Example 1, except that the raw materials shown in Table 2 - 2 were used at the described compounding ratios.

[0089]

Table 2

[0090]

Table 2

[0091] <Evaluation methods and criteria> Each of the active energy ray curable compositions obtained in the above Examples and Comparative Examples was printed using a sheet-fed printing machine "Lithrone 26 (manufactured by Komori Corporation)". First, a UV-curable offset ink "FD Carton X Ink M (manufactured by Toyo Ink Co., Ltd., containing a multifunctional (meth)acrylic monomer having three or more functionalities)" was printed on the paper substrate Aurora Coat (coated paper high gloss type, paper thickness 81 μm, manufactured by Nippon Paper Industries Co., Ltd.) so that the ink density was 1.75 (measuring device: X-Rite eXact (manufactured by X-Rite Co., Ltd.), conditions: Illuminant D50, standard observer 2°, density status E, no filter), and cured with a UV lamp. The printing speed of the above printing was 8000 sheets / hour, the types of UV lamps were two air-cooled metal halide lamps and one high-pressure mercury lamp, and the intensity of the UV lamps was 160 W / cm for all three lamps (accumulated light quantity 450 mJ / cm 2 ). Next, each active energy ray curable composition (S1 to S26, T1 to T5) was applied onto the FD Carton X ink M print obtained above using a Lithrone 26 flexo coating unit, and cured with a UV lamp to obtain the corresponding laminate (G1 to G26, H1 to H5). The anilox roll of the coating unit had a trihelical engraved pattern, a line count of 90 lines / inch, and a cell volume of 25 ml / m. 2 During flexo coating, the printing speed was 8000 sheets / hour, and the temperature of the S1 liquid was controlled to 25°C. The type, number, and intensity of the UV lamps were the same as those used for the curing conditions of FD Karton X Ink M described above.

[0092] <Viscosity stability> For the active energy ray-curable compositions obtained in the examples and comparative examples, the viscosity change rate was measured. The viscosity change rate is a value obtained by measuring the viscosity before and after heating, dividing the viscosity after heating by the viscosity before heating, and expressing the result as a percentage of 100. For the above-mentioned heating, the process is as follows: After pouring the active energy ray-curable composition into a cylindrical metal container with an inner diameter of 9.6 cm and a height of 3.0 cm to a thickness of 1 cm, it is left in an environment at 40 °C for 30 minutes. For the viscosity measurement, it was measured using a cone-plate viscometer under the condition that the liquid temperature was 25 °C. The evaluation criteria are as follows. 5 (excellent): Viscosity change rate is 0% or more and less than 3% 4 (good): Viscosity change rate is 3% or more and less than 6% 3 (fair): Viscosity change rate is 6% or more and less than 9% 2 (poor): Viscosity change rate is 9% or more and less than 12% 1 (inferior): Viscosity change rate is 12% or more Note that the practically applicable evaluations are 3, 4, and 5.

[0093] <Adhesion> For the laminates obtained in the examples and comparative examples, 100 cross-cuts of 1 mm were made on the cured layer using a checkerboard peeling test jig. 2 After that, an adhesive tape (LP24, manufactured by Nichiban Co., Ltd.) was attached to the cross-cuts and peeled off in the 90-degree direction, and the number of remaining checkerboard squares on the cured layer was measured. The evaluation criteria are as follows. 5 (excellent): Number of remaining checkerboard squares = 100 (no peeling) 4 (good): Number of remaining checkerboard squares = 96 or more and less than 100 3 (fair): Number of remaining checkerboard squares = 90 or more and less than 96 2 (poor): Number of remaining checkerboard squares = 86 or more and less than 90 1 (inferior): Number of remaining checkerboard squares = less than 86 Note that the practically applicable evaluations are 3, 4, and 5.

[0094] <Abrasion resistance> For the laminates obtained in the examples and comparative examples, they were set on a Sutherland Rub Tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) so that the cured layers were in contact with each other, a load of 2 pounds was applied, and after reciprocating a predetermined number of times, the abrasion resistance was evaluated by visually checking whether the cured layer peeled off and the base layer was visible. The evaluation criteria are as follows. 5 (excellent): Even after 10,000 reciprocations, the cured layer did not peel off and the base layer was not visible. 4 (good): After 10,000 reciprocations, the cured layer peeled off and the base layer was visible, but after 9,000 reciprocations the base layer was not visible. 3 (fair): After 9,000 reciprocations, the cured layer peeled off and the base layer was visible, but after 8,000 reciprocations the base layer was not visible. 2 (poor): After 8,000 reciprocations, the cured layer peeled off and the base layer was visible, but after 7,000 reciprocations the base layer was not visible. 1 (inferior): Even after 7,000 reciprocations, the cured layer peeled off and the base layer was visible. Note that the practically usable evaluations are 3, 4, and 5.

[0095] <Moisture and heat resistance> After exposing the laminates obtained in the examples and comparative examples to an atmosphere of 60°C and 90% humidity for 48 hours, 100 cross-cuts of 1 mm were made on the cured layer using a cross-cut peel test jig. 2 Thereafter, an adhesive tape (LP24, manufactured by Nichiban Co., Ltd.) was attached to the cross-cuts and peeled off in the 90-degree direction, and the number of remaining cross-cut squares of the cured layer was measured. The evaluation criteria are as follows. 5 (excellent): Number of remaining cross-cut squares = 90 or more 4 (good): Number of remaining cross-cut squares = 80 or more and less than 90 3 (fair): Number of remaining cross-cut squares = 75 or more and less than 80 2 (poor): Number of remaining cross-cut squares = 70 or more and less than 75 1 (inferior): Number of remaining cross-cut squares = less than 70 Note that the practically usable evaluations are 3, 4, and 5.

[0096] A practically usable active energy ray-curable composition simultaneously satisfies stable printing suitability and good film physical properties. That is, it simultaneously satisfies having an evaluation of 3 or more in terms of viscosity stability and an evaluation of 3 or more in all items of adhesion, abrasion resistance, and heat and humidity resistance.

[0097] From the above examples, an active energy ray-curable composition containing a polyfunctional urethane (meth)acrylate, a monofunctional ethylenically unsaturated monomer, and resin fine particles, wherein the weight average molecular weight of the polyfunctional urethane (meth)acrylate is 3000 to 20000, and the hydroxyl value of the solid content of the active energy ray-curable composition is 30 mgKOH / g or less, so that an active energy ray-curable composition having good printing suitability (viscosity stability) and excellent cured film physical properties such as adhesion, abrasion resistance, and heat and humidity resistance could be obtained.

Industrial Applicability

[0098] Since no organic solvent is blended or it can be reduced, this active energy ray-curable composition is useful as a low-luster coating agent with a low environmental load.

Claims

1. An active energy ray-curable matte coating composition containing a polyfunctional urethane (meth)acrylate, a monofunctional ethylenically unsaturated monomer, and resin fine particles, wherein the polyfunctional urethane (meth)acrylate has a weight average molecular weight of 3,000 to 20,000 and is contained in an amount of 5 to 40% by mass based on the total mass of the active energy ray-curable matte coating composition, the monofunctional ethylenically unsaturated monomer is contained in an amount of 30 to 60% by mass based on the total mass of the active energy ray-curable matte coating composition, the resin fine particles have a volume average particle diameter of 1 to 10 μm and are contained in an amount of 10 to 40% by mass based on the total mass of the active energy ray-curable matte coating composition, and the active energy ray-curable matte coating composition has a hydroxyl value of the solid content of 30 mgKOH / g or less. (However, this does not include the case where the resin fine particles are black resin particles.)

2. The active energy ray-curable matte coating composition according to claim 1, wherein the monofunctional ethylenically unsaturated monomer has a heterocyclic structure.

3. The active energy ray-curable matte coating composition according to claim 1, further containing a photopolymerization initiator.

4. The active energy ray-curable matte coating composition according to claim 1, wherein the polyfunctional urethane (meth)acrylate has a structural unit derived from a polyether.

5. The active energy ray-curable matte coating composition according to claim 1, wherein the resin fine particles are urethane resin fine particles.

6. The active energy ray-curable matte coating composition according to claim 1, further containing a silicon acrylate.

7. The active energy ray-curable matte coating composition according to claim 1, which is for a paper substrate. Claim 8 A laminate having a printing layer and a cured layer formed from the active energy ray curable matte coating according to any one of claims 1 to 7 on a paper substrate. Claim 9 A method for producing a laminate, wherein the active energy ray curable matte coating according to any one of claims 1 to 7 is applied and cured on a substrate by any one of flexographic printing, screen printing, and roll coating.

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