Water-based primer composition, packaging material laminate, and method for manufacturing packaging material laminate

Abstract

The present invention aims to provide a water-based primer composition, a packaging material laminate, and a method for producing a packaging material laminate, the water-based primer composition being excellent in transferability to a paper base material and an ink layer, in leveling property, in color spot (uneven gloss) resistance when a active energy ray-curable composition is applied on the water-based primer layer, and in a cosmetic appearance (matte property) of the packaging material laminate. The present invention relates to a water-based primer composition, which is a water-based primer composition for forming a primer layer of a packaging material laminate having, in order, a paper base material, a primer layer, and an active energy ray-curable layer, the water-based primer composition comprising a binder resin, a body pigment, and a water-based solvent.

Description

TECHNICAL FIELD

[0001] The present application relates to a water-based primer composition, a packaging material laminate, and a method for producing a packaging material laminate.

[0002] More specifically, the present application relates to a water-based primer composition for forming a primer layer of a packaging material laminate having, in order, a paper base material, a primer layer, and a layer cured by active energy rays, the packaging material laminate, and a method for producing the packaging material laminate. BACKGROUND

[0003] In recent years, in the field of packaging using a paper base material (also referred to as a paper product), research on applying a top coating varnish to a printed matter after printing a color ink on a variety of base materials for the purpose of imparting durability and a cosmetic property to the printed matter is widely performed. In the field of paper product packaging, when displayed on a store shelf after printing, glossiness is sometimes required for cosmetic property, and matting (matt) property is sometimes required. In particular, in recent years, the demand for printed matters with a matting effect has increased. In addition, in the field of paper product packaging, top coating varnishes are particularly used for packaging of high-grade cosmetics and the like. The appearance (cosmetic property) quality of a printed matter has an influence on the purchasing desire of a customer due to the expression of a high-grade feeling, and thus it is extremely important to guarantee the quality. Note that, in addition to a top coating varnish, there are other markings such as an overprint (OP) varnish, but the same is used synonymously with a top coating varnish.

[0004] In addition, as a function of a top coating varnish, not only appearance such as glossiness and matting (matt) property of a printed matter, but also durability for protecting a printed pattern portion is required. Therefore, a coating liquid of an active energy ray-curable type having excellent film strength is widely used.

[0005] As a top coating varnish having a matting effect, various kinds of fine particles are added to a coating liquid in most cases. A top coating varnish forms a concave-convex by fine particles present on the surface of a dried or cured coating film, diffusely reflects light at the interface, and thereby imparts a matt feeling. On the other hand, in the case where a base material is a paper base material, since solvents, low-molecular components, resin components, and the like in a top coating varnish penetrate into the base material, or transfer or leveling at the time of printing is poor, a portion where fine particles exist in large amounts and a portion where fine particles do not exist so much are formed like a pattern, and thus there are problems that unevenness of glossiness value and unevenness of printed appearance (color spots) are easily generated.

[0006] In order to suppress the penetration of the top coat varnish into the paper base material, a primer layer is provided under the top coat layer in most cases. For the primer, the demand for a water-based type primer (water-based primer) is still high from the viewpoint of reducing the load on the working environment and strengthening the chemical substance management restrictions in each country in recent years, and protecting the global environment, rather than using an oil-based type using an organic solvent. Note that, in addition to the primer, anchor varnish, caulking varnish, and the like are also used synonymously with the primer.

[0007] Patent Document 1 proposes a laminate obtained by applying a water-based anchor varnish containing a styrene-butadiene rubber emulsion having a glass transition temperature of 5°C to a water-based printing ink layer printed on a paper base material, and then applying an overprint varnish of a live energy ray-curable type.

[0008] In addition, Patent Document 2 proposes a method of sequentially laminating a solid-colored layer, a primer layer formed of a two-liquid curing type urethane resin composed of an acrylic polyol and an isocyanate, and then laminating a surface protective layer on a fibrous base material. However, in Patent Documents 1 and 2, there are problems in the transferability, leveling property, and transfer, leveling property, and matting property (matte feeling) of the live energy ray-curable composition to the water-based primer layer on the ink layer.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2007-45962

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 2005-89932 SUMMARY

[0013] PROBLEMS TO BE SOLVED BY THE INVENTION

[0014] An object of the present application is to provide a water-based primer composition excellent in transferability to a paper base material and an ink layer, and in leveling property, excellent in color spot resistance (resistance to gloss unevenness) when a live energy ray-curable composition is applied to the water-based primer layer, and to provide a laminate for packaging materials excellent in makeup appearance (matting property).

[0015] METHOD FOR SOLVING THE PROBLEMS

[0016] Embodiments of the present application include the following. However, the present application is not limited to the following embodiments, but includes various embodiments.

[0017] <1> An aqueous primer composition for forming a primer layer of a laminate for packaging material having a paper substrate, the primer layer, and a layer cured by active energy rays in this order, comprising a binder resin, a body pigment, and a water-based solvent.

[0018] <2> The aqueous primer composition according to <1> above, wherein the surface tension is 24 to 38 mN / m.

[0019] <3> The aqueous primer composition according to <1> or <2> above, wherein the surface free energy of the primer layer is 24 to 40 dyne / cm.

[0020] <4> The aqueous primer composition according to any one of <1> to <3> above, wherein the water-based solvent comprises a hydrophilic organic solvent.

[0021] <5> The aqueous primer composition according to any one of <1> to <4> above, wherein the viscosity of the aqueous primer composition is 50 to 2,500 mPa-s.

[0022] <6> The aqueous primer composition according to any one of <1> to <5> above, wherein the binder resin comprises at least one selected from the group consisting of an aqueous acrylic resin (A), an aqueous urethane resin (B), and an aqueous polyester resin (C).

[0023] <7> The aqueous primer composition according to any one of <1> to <6> above, wherein the body pigment comprises at least one selected from the group consisting of silicon dioxide, calcium carbonate, barium sulfate, and talc.

[0024] <8> The aqueous primer composition according to any one of <1> to <7> above, wherein the average particle diameter of the body pigment is 1 to 10 μm.

[0025] <9> The aqueous primer composition according to any one of <4> to <8> above, wherein the boiling point of the hydrophilic organic solvent is 70 to 90°C.

[0026] <10> The aqueous primer composition according to any one of <1> to <9> above, which is used for flexographic printing or gravure printing.

[0027] <11> A laminate for packaging material having a paper substrate, a primer layer formed from the aqueous primer composition described above, and a layer cured by active energy rays in this order, wherein the layer cured by active energy rays comprises resin fine particles.

[0028] <12> The laminate for packaging material according to <11> above, further comprising an offset printing layer.

[0029] <13> The laminate for packaging material according to <11> or <12> above, wherein the 60° specular gloss of the active energy ray-cured layer is 40 or less.

[0030] <14> A method for producing a laminate for packaging material having a paper base material, a primer layer, and an active energy ray-cured layer in this order, the method comprising a step of forming the primer layer by flexographic printing or gravure printing an aqueous primer composition containing a binder resin, a body pigment, and a water-based solvent on the paper base material, and a step of forming the active energy ray-cured layer by printing an active energy ray-curable composition on the primer layer and then irradiating active energy rays.

[0031] Effects of the Invention

[0032] According to the present application, an aqueous primer composition which is excellent in transferability to a paper base material and an ink layer, and in leveling property, and which is excellent in color spot resistance (resistance to gloss unevenness) when an active energy ray-cured composition is applied on the aqueous primer layer, and a laminate for packaging material which is excellent in makeup appearance (matte property) and in wiping resistance are provided. DETAILED DESCRIPTION

[0033] Hereinafter, the embodiments of the present application will be described in detail, and the description of the components recited below is an example (representative example) of the embodiments of the present application, and the present application is not limited to these contents as long as the gist thereof is not exceeded.

[0034] In the present specification, the "aqueous primer composition" is sometimes simply referred to as "primer composition", but is synonymous. The "laminate for packaging material" is sometimes simply referred to as "laminate", but is synonymous. In addition, in the specification, "mN / m" is used as the unit of the surface tension of a liquid such as a primer composition, and "dyne / cm" is used as the unit of the surface tension, i.e., surface free energy, of a solid such as a primer layer. The units are different but the values are the same, and for example, when the surface energy of a primer layer is compared with the surface tension of an active energy ray-cured composition, the values can be directly compared.

[0035] Hereinafter, the present application will be described in detail.

[0036] <Water-based Primer Composition>

[0037] The present application relates to a water-based primer composition, which is a water-based primer composition for forming a primer layer of a laminate for packaging material having a paper base material, a primer layer, and a layer cured by active energy rays in this order, the water-based primer composition comprising a binder resin, a body pigment, and a water-based solvent. The water-based primer composition is preferably used in a manner as a primer layer of a layer cured by active energy rays on a paper base material and / or an ink layer formed on a paper base material as occasion demands. By the water-based primer composition containing a body pigment, penetration of a composition curable by active energy rays for forming a layer cured by active energy rays into a paper base material is suppressed, and ink adhesion, leveling stability of the layer cured by active energy rays are improved, so that gloss unevenness (mottle) is less likely to occur, and a uniform and high-class appearance (matt appearance) can be obtained. If the surface tension of the water-based primer composition is 24 to 38 mN / m, the above effects are more easily obtained, and thus are preferred. However, the above effects are found based on the investigation, and the present application is not particularly limited thereto.

[0038] (Surface tension of water-based primer composition)

[0039] In the present application, the surface tension of the water-based primer composition is preferably 24 to 38 mN / m, more preferably 26 to 36 mN / m, and further preferably 27 to 33 mN / m. If it is 24 mN / m or more, reduction in surface free energy of the primer layer is prevented, and transfer, ink adhesion, and leveling of a composition curable by active energy rays on the primer layer are improved. If it is 38 mN / m or less, wettability to a paper base material and an ink layer is improved, and shrinkage is suppressed.

[0040] As a method of adjusting the surface tension of the water-based primer composition to the above range, a method of adjusting the kind and the amount of addition of the body pigment can be mentioned, and the body pigment can be used in the preferred manner described below, for example. In addition, if a hydrophilic organic solvent is added, the surface tension tends to be reduced, and the hydrophilic organic solvent is preferably used in the preferred manner described below. In addition, the surface tension can be adjusted by an additive such as a surface modifier, and if the surface modifier is added, the surface tension tends to be reduced. The surface tension can be adjusted to the prescribed range by appropriately selecting these methods.

[0041] When only additives are used to adjust the surface tension of a water-based primer composition, the additives remain in the primer layer formed by printing and drying the composition, reducing the surface free energy of the primer layer. Therefore, when printing an active energy radiation-cured composition onto the primer layer, poor leveling is easily achieved. Therefore, by incorporating a hydrophilic organic solvent into the water-based primer composition, the surface tension of the water-based primer composition is reduced. On the other hand, the solvent evaporates after drying without leaving residue in the primer layer, thus not reducing the surface free energy of the primer layer. Therefore, it is easier to achieve both leveling of the water-based primer composition on paper substrates and ink layers and leveling of the active energy radiation-cured composition on the primer layer, which is therefore more preferable. The above-described functions are based on investigation and do not specifically limit the invention of this application.

[0042] (Methods for measuring surface tension)

[0043] Surface tension can be measured, for example, using a high-precision surface tension meter DY-700 (manufactured by Kyowa Interface Chemical Co., Ltd.). In this invention, the liquid temperature during measurement is set to 25°C.

[0044] <Primer layer>

[0045] The primer layer of the present invention is formed from an aqueous primer composition. The surface energy of the primer layer is preferably 24–40 dyne / cm, more preferably 26–38 dyne / cm, and even more preferably 30–38 dyne / cm. If within the above range, the surface energy of the primer layer is lower than the surface tension of the active energy ray curing composition, resulting in good wetting and spreading of the active energy ray curing composition on the primer layer. If it is 24 dyne / cm or higher, the transfer, ink adhesion, and leveling properties of the active energy ray curing composition to the aqueous primer layer become good. If it is 40 dyne / cm or lower, the surface tension of the primer composition decreases accordingly, thus achieving a good matte finish by suppressing pinholes on the substrate and ink layer.

[0046] As a method to achieve the surface free energy of the primer layer within the aforementioned range, methods such as adjusting the type and amount of extender pigment can be employed, and the preferred method described later can be used. Furthermore, if the amount of extender pigment increases, the surface free energy tends to increase; if the particle size of the extender pigment decreases, the surface free energy also tends to increase. Additionally, methods such as selecting the type of binder resin or adjusting with additives such as surface conditioners can be employed, and these methods can be appropriately selected to adjust the surface free energy to the specified range.

[0047] To ensure the surface free energy of the primer layer is within the aforementioned range, the adhesive resin preferably contains at least one selected from the group consisting of a waterborne acrylic resin (A), a waterborne urethane resin (B), and a waterborne polyester resin (C), wherein waterborne acrylic resin (A) is suitable, and two or more resins can be used together without impairing the effects of the present invention. By using the above-mentioned adhesive resin, a balance between the surface free energy of the primer layer and the surface tension of the active energy ray curing composition is easily achieved, resulting in good transfer, ink adhesion, and leveling properties of the active energy ray curing composition to the primer layer. The mass ratio of the adhesive resin in the waterborne primer composition is preferably 10-50% by mass, more preferably 20-40% by mass. The mass ratio of the adhesive resin in the primer layer is preferably 60-95% by mass, more preferably 70-85% by mass.

[0048] (Methods for determining surface free energy)

[0049] Here, the surface free energy mentioned above is defined as "the free energy per unit area of ​​the surface," which is the excess energy possessed by the surface of the primer layer compared to the interior (body) of the layer. The greater the surface free energy of a solid, the easier it is for gases or particles to be adsorbed, for liquids to be easily wetted, and for it to adhere to other solids. Surface free energy can be measured using a contact angle meter, etc., by analyzing the contact angle between water and hexadecane using the Kaelble-Uy method. In this invention, the surface free energy of the primer layer mentioned above is calculated using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd., by the following method. First, 1 μL of water (pure water) is dropped onto the surface of the primer layer, and the contact angle is measured after 30 seconds. Then, the contact angle is measured again using hexadecane instead of water. The surface free energy is calculated using the obtained contact angles of water and hexadecane by the Kaelble-Uy method.

[0050] <Adhesive Resins>

[0051] The adhesive resin can be any known resin. From the viewpoint of substrate adhesion and film strength of the primer layer, it is preferably selected from at least one of the group consisting of waterborne acrylic resin (A), waterborne urethane resin (B), and waterborne polyester resin (C), wherein waterborne acrylic resin (A) is preferred. Furthermore, two or more resins may be used together without impairing the effects of the present invention.

[0052] The mass ratio of the binder resin in the water-based primer composition is 10 to 50% by mass, more preferably 20 to 40% by mass. Within the above range, the matte finish and abrasion resistance become good.

[0053] (Waterborne acrylic resin (A))

[0054] Waterborne acrylic resin (A) refers to the general term for waterborne acrylic emulsion (A1) and water-soluble acrylic resin (A2) (excluding resins containing urethane bonds). Waterborne acrylic resin (A) is a resin containing (meth)acrylate units, including polymers or copolymers of acrylic monomers such as alkyl (meth)acrylate, (meth)acrylic acid, and (meth)acrylamide, as well as copolymers of the above acrylic monomers with monomers such as styrene and maleic anhydride. It should be noted that acrylic monomers may have functional groups such as hydroxyl, carboxyl, and glycidyl groups. Examples of acrylic monomers include acrylates and methacrylates. For instance, examples of acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and glycidyl acrylate. Examples of methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and glycidyl methacrylate. Additionally, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and other carboxylic acid monomers or their anhydrides and half-esters can also be used.

[0055] The acrylic monomers preferably include methyl acrylate, ethyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Additionally, examples of styrene monomers constituting styrene-acrylic resins include styrene, α-methylstyrene, and β-methylstyrene. Among these, α-methylstyrene is preferred.

[0056] The mass ratio of waterborne acrylic resin (A) in the adhesive resin is preferably 60-100% by mass, more preferably 80-100% by mass, and particularly preferably 90-100% by mass. Within the above range, the adhesion and scratch resistance become good.

[0057] (Water-based acrylic emulsion (A1))

[0058] The aqueous acrylic emulsion (A1) comprises at least one selected from styrene-acrylic emulsion resins and acrylic emulsion resins (excluding styrene-acrylic emulsion resins). Preferably, it comprises a styrene-acrylic emulsion resin. The acrylic monomer constituting the acrylic resin can preferably be the same monomer as described above. It should be noted that an emulsion refers to a resin that is insoluble or sparingly soluble in water, but is stabilized by dispersing the resin into small particles. Alternatively, a copolymer emulsion obtained by copolymerizing the above monomers using a water-soluble acrylic resin as a polymeric emulsifier can also be preferred.

[0059] The average particle size of the aqueous acrylic emulsion (A1) is preferably 10–500 nm, more preferably 20–300 nm, and even more preferably 30–250 nm. The average particle size can be determined, for example, as the D50 value based on dynamic light scattering. Furthermore, the weight-average molecular weight of the aqueous acrylic emulsion (A1) is preferably 2000–2000000, more preferably 5000–1500000, and even more preferably 10000–100000. This is because, within the above range, the cohesiveness of the coating film is improved, and the abrasion resistance is improved. As the aforementioned styrene-acrylic resin, examples include Joncryl PDX-7734 (Tg 40°C, solids content 41.4% by mass) and Joncryl PDX-7538 (Tg 75°C, solids content 45.5% by mass) manufactured by BASF. Additionally, as acrylic resins, Joncryl 60J, 70J, and HPD-196 manufactured by BASF can be used.

[0060] (Water-soluble acrylic resin (A2))

[0061] The water-soluble acrylic resin (A2) is preferably selected from at least one of styrene-acrylic resin and acrylic resin (excluding styrene-acrylic resin), and has hydrophilic groups such as carboxyl groups. Furthermore, a water-soluble resin in which the hydrophilic groups are solubilized by an alkaline compound is preferred. Examples of the alkaline compound include amine compounds and alkali metals. Specifically, examples of the amine compounds include alkylamines such as ammonia, diethylamine, triethylamine, and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine, and triethanolamine. Examples of the alkali metals include sodium hydroxide and potassium hydroxide.

[0062] The acid value of the water-soluble acrylic resin (A2) is preferably 150–300 mg KOH / g, more preferably 180–260 mg KOH / g. Within this range, the dispersion stability of the extender pigment is improved, the leveling properties during transfer are good, and the resistance to color spots is good. The weight-average molecular weight of the water-soluble acrylic resin (A2) is preferably 1500–60000, more preferably 4000–30000. Within this range, the dispersion stability of the extender pigment is improved, the leveling properties during transfer are good, and the resistance to color spots is good. Examples of water-soluble acrylic resins (A2) include AQURYS TYS-85, TYS-3000, and LH52 manufactured by Gifu Shellac Manufacturing Co., Ltd., and Joncryl 60J, 70J, HPD-196, and HPD-96J manufactured by BASF.

[0063] In the waterborne primer composition of the present invention, the waterborne acrylic resin (A) contains at least one selected from the group consisting of a waterborne acrylic emulsion (A1) and a water-soluble acrylic resin (A2). In some embodiments, the waterborne acrylic resin (A) preferably contains a waterborne acrylic emulsion (A1), and more preferably further contains a water-soluble acrylic resin (A2).

[0064] In some embodiments, the mass ratio (A1 / A2) of the aqueous acrylic emulsion (A1) to the water-soluble acrylic resin (A2) in the aqueous acrylic resin (A) is preferably 95 / 5 to 50 / 50, more preferably 90 / 10 to 60 / 40. Furthermore, in some embodiments, the above-mentioned mass ratio (A1 / A2) is preferably 90 / 10 to 30 / 70, more preferably 80 / 20 to 35 / 65, and particularly preferably 70 / 30 to 40 / 60.

[0065] With the above-mentioned mass ratio within the above-mentioned range, it tends to be easier to improve the seal and abrasion resistance.

[0066] (Waterborne urethane resin (B))

[0067] The term "waterborne urethane resin (B)" is not limited to any waterborne resin containing urethane bonds; it is a general term for both waterborne urethane emulsions (B1) and water-soluble urethane resins (B2). Furthermore, embodiments in which the waterborne urethane resin (B) further contains urea bonds are preferred.

[0068] In this invention, the aqueous urethane resin (B) comprises a urethane acrylic resin containing both an acrylic resin portion and a urethane resin portion. Furthermore, embodiments having urea bonds are preferred.

[0069] As for the waterborne urethane resin (B), the following forms are preferred: a urethane resin synthesized from polyols, polyhydroxy acids, and polyisocyanates; and a urethane urea resin, as one embodiment of the waterborne urethane resin, which is a urethane resin obtained by chain extension of a urethane prepolymer with isocyanate groups at the ends, synthesized from polyols, polyhydroxy acids, and polyisocyanates, and a polyamine. In the manufacture of the water-soluble urethane resin (B2), when reacting the polyol with the polyisocyanate, it is preferable to introduce acidic groups such as carboxyl groups and sulfone groups into the resin, neutralize it with a basic compound, and thereby achieve water solubility. From the viewpoint of water resistance, carboxyl groups are preferred as this acidic group.

[0070] (Polyols)

[0071] The polyols mentioned above are not limited to the following, and examples preferably include polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polyolefin polyols, dimerols, hydrogenated dimerols, etc. These polyols can be used alone or in combination of two or more. The aqueous urethane resin preferably contains a structural unit composed of at least one polyol selected from polyester polyols, polyether polyols, and polycarbonate polyols. More preferably, the polyol is a polyester polyol, a polyether polyol, or a polycarbonate polyol. The number average molecular weight of the polyol is preferably between 500 and 5000.

[0072] (Polyether polyols)

[0073] Examples of the aforementioned polyether polyols include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and copolymers thereof. The aqueous urethane resin preferably comprises structural units composed of polyether polyols. In one embodiment, the aqueous urethane resin (B) preferably contains structural units derived from polyethylene glycol, and preferably contains 0.1 to 25% by mass of structural units derived from polyethylene glycol in the total mass of the aqueous urethane resin, more preferably 2 to 15% by mass, and even more preferably 2 to 10% by mass.

[0074] (Polyester polyols)

[0075] The aforementioned polyester polyol preferably has a form derived from the structural unit of a polyester polyol that is a condensation product of a diacid and a branched diol. The diacid is preferably sebacic acid, adipic acid, succinic acid, etc., and the branched diol refers to a form in which at least one hydrogen atom on the carbon atom of an alkylene diol has a substituent. Specifically, it is preferable to contain at least 50% by mass of at least one selected from propylene glycol, 3-methyl-1,5-pentanediol, neopentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol, more preferably at least 60% by mass. However, the embodiments of the polyester polyol are not limited to these.

[0076] (Polycarbonate polyols)

[0077] The polycarbonate polyols described above are not limited to specific manufacturing methods or the types of diols constituting the polycarbonate polyols; preferred examples include condensation polymers produced by transesterification of a diol composed of alkylene glycols with a carbonate compound. Furthermore, alicyclic and / or aliphatic polycarbonate diols are preferred.

[0078] Examples of the aforementioned diols preferably include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, neopentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butynediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanediol, diethylene glycol, polypropylene glycol, and dipropylene glycol. These can be used alone or in combination of two or more. Polycarbonate polyols having diol structures with other branched structures, such as 3-methyl-1,5-pentanediol, are preferred. The carbonate compound is not particularly limited, and examples include dialkyl carbonate, diaryl carbonate, or alkylene carbonate. Specific examples of carbonate compounds include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dibutyl carbonate, diaryl carbonates such as diphenyl carbonate, and alkylene carbonates such as ethylene carbonate.

[0079] (Polyisocyanates)

[0080] Examples of the aforementioned polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. It should be noted that they can also be trimers forming an isocyanurate ring structure. Examples of aromatic diisocyanates include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenyl diisocyanate, 1,4-phenyl diisocyanate, and toluene diisocyanate. Examples of aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, xylylenediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(methyl isocyanate)cyclohexane, methylcyclohexane diisocyanate, norbornene diisocyanate, m-tetramethylxylylenediisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, and dimer diisocyanates formed by converting the carboxyl group of a dimer acid to an isocyanate group. Preferably, at least one of toluene diisocyanate, isophorone diisocyanate, xylylenediisocyanate, bis(methyl isocyanate)cyclohexane, hexamethylene diisocyanate, and a trimer of hexamethylene diisocyanate is selected. These polyisocyanates can be used alone or in combination of two or more.

[0081] (Polyhydroxy acid)

[0082] The aforementioned polyhydroxy acids are not limited to any of the following: polyols containing carboxyl groups can be used. Examples of preferred polyhydroxy acids include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolpentanoic acid, etc. These can be used alone or in combination of two or more. The polyhydroxy acids are used in the manufacturing process of waterborne urethane resins, introducing their carboxyl groups into the resulting urethane resin, giving it an acid value. Unreacted carboxyl groups are neutralized, thus achieving waterborneity.

[0083] (Polyamines)

[0084] The compounds that can be used as the aforementioned polyamines are various known amines, such as preferably 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propanediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl propanediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, ethylenediamine, propanediamine, hexamethylenediamine, isophorone diamine, dicyclohexylmethane-4,4'-diamine, and dimer diamines that convert the carboxyl group of a dimer acid to an amino group, etc., which can be used alone or in combination of two or more.

[0085] (Reaction Terminator)

[0086] It can also be used in conjunction with the above-mentioned polyamines as a reaction terminator. Examples of such reaction terminators include dialkylamines such as di-n-butylamine, amines with hydroxyl groups such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, 2-amino-2-ethyl-1-ethyl-1,3-propanediol, N-di-2-hydroxyethylethylenediamine, N-di-2-hydroxyethylpropanediamine, and N-di-2-hydroxypropylethylenediamine, as well as monoamine amino acids such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminohexanoic acid, aminobenzoic acid, aminoisophthalic acid, and aminosulfonic acid.

[0087] (Neutralizing agent)

[0088] To make the waterborne urethane resin (B) waterborne, it is preferable to neutralize the carboxyl groups in the resin with an alkaline compound.

[0089] (Alkaline compound)

[0090] Examples of basic compounds include ammonia; organic amines such as monoethylamine, diethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, and 2-amino-2-ethyl-1-propanol; and inorganic bases such as sodium hydroxide and potassium hydroxide. One or more of these compounds can be used, but to improve the water resistance of the dried film, water-soluble substances with high volatility that readily dissociate due to heat are preferred, especially ammonia, trimethylamine, and triethylamine. Furthermore, the acid value of the above-mentioned waterborne urethane resin (B) is preferably 5–100 mg KOH / g, more preferably 10–60 mg KOH / g. These acid values ​​are neutralized by the above-mentioned basic compounds to make the resin waterborne.

[0091] When the aqueous urethane resin (B) is an urethane acrylic resin, the acrylic resin portion and the urethane resin portion can be alternating copolymers, or they can be so-called graft polymers where the main chain is an urethane resin portion and the side chain is an acrylic resin portion, or vice versa. The aqueous urethane emulsion resin (B1) can be a core / shell type with an acrylic resin portion in the core and an urethane resin portion in the shell, or it can be an island structure with an acrylic resin portion in the sea portion and an urethane resin portion in the island portion.

[0092] The average particle size of the aqueous urethane emulsion (B1) is preferably in the range of 20 nm to 400 nm, and more preferably in the range of 30 nm to 200 nm.

[0093] Specific examples of waterborne carbamate emulsions (B1) include Takelac W-5030, W-5661, W-6010, W-6020, W-6061, W-6355, W-605, WPB-341(30), WS-4022 (manufactured by Mitsui Chemicals Co., Ltd.), WEM-200U, WEM-3000, WEM-505C (manufactured by Taisei Fine Chemicals Co., Ltd.), AQUABRID46777, 3756, UX-100, UX-110, AST531, AST49 (manufactured by Daisei Miwa Co., Ltd.), etc.

[0094] Waterborne urethane resin (B2) can be appropriately manufactured by known methods. For example, the acetone method using an inactive and hydrophilic organic solvent for isocyanate, and solvent-free synthesis methods that do not use any solvent at all, can be cited. For example, the method described in Japanese Patent Application Publication No. 2013-234214 can be appropriately used.

[0095] (Waterborne polyester resin (C))

[0096] The waterborne polyester resin (C) is preferably a polyester resin synthesized through a polycondensation reaction (esterification reaction) of a polyacid and / or its anhydride with a polyol. This reaction can be carried out under normal or reduced pressure. Furthermore, the molecular weight can be adjusted by adjusting the ratio of the polyacid and / or its anhydride to the polyol (excess ratio: the equivalent ratio of hydroxyl groups to acid groups). Examples of water-soluble methods include introducing carboxyl groups from copolymers of acrylic acid and methacrylic acid, or introducing sulfonic acid groups from metal salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, and 4-sulfonnaphthalene-2,7-dicarboxylic acid-5[4-sulfophenoxy]isophthalic acid, or sulfonic acid groups from these ester-forming derivatives. Examples of metal salts include salts of Li, Na, K, Mg, Ca, Cu, and Fe. Sodium 5-sulfoisophthalate and dimethyl-5-sulfoisophthalate are particularly preferred.

[0097] (polyacids and / or their anhydrides)

[0098] As for the polybasic acids and / or their anhydrides that can be used in the synthesis of waterborne polyester resin (C), diabasic acids and / or their anhydrides are preferred. Specifically, examples include aromatic diabasic acids and their anhydrides such as terephthalic acid, isophthalic acid, and phthalic anhydride; alicyclic diabasic acids and their anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 1,4-cyclohexanedicarboxylic acid; and aliphatic diabasic acids and their anhydrides such as succinic acid (anhydride), fumaric acid, maleic acid (anhydride), adipic acid, sebacic acid, azelaic acid, and humic acid. The appropriate one can be selected from these, taking into account the surface tension, surface free energy, flexibility, and adhesion of the resulting coating.

[0099] (Polyols)

[0100] In addition, examples of the aforementioned polyols include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylolpropane, octanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, and 2-ethyl-1,3-hexanediol. The appropriate polyol can be selected from these, taking into account the surface tension, surface free energy, flexibility, and adhesion of the resulting coating.

[0101] The aforementioned waterborne polyester resin (C) is preferably supplied in the preparation of the waterborne primer composition of the present invention in the form of a solution dissolved in a solvent. As the solvent, water and / or a hydrophilic organic solvent that can dilute the polyester resin can preferably be used. Examples include alcohols such as methanol, ethanol, propanol, and butanol; glycol ethers such as ethylene glycol (mono- and dimethyl) ether, ethylene glycol (mono- and diethyl) ether, ethylene glycol monobutyl ether, diethylene glycol (mono- and dimethyl) ether, diethylene glycol (mono- and diethyl) ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono- and dimethyl) ether, propylene glycol (mono- and dimethyl) ether, and dipropylene glycol (mono- and dimethyl) ether.

[0102] The acid value of the waterborne polyester resin (C) is preferably 80 mg / g or less, more preferably 60 mg / g or less, and even more preferably 40 mg / g or less. Within this range, the hydrolysis of the polyester is suppressed, allowing the molecular weight to be maintained at a high level, thereby improving the cohesiveness of the coating film and thus resulting in good abrasion resistance. The acid value can be varied depending on the types of polyester polyol and tetracarboxylic dianhydride used; therefore, those skilled in the art can easily select the types of polyester polyol and tetracarboxylic dianhydride to fall within the aforementioned preferred range.

[0103] The weight-average molecular weight of the aforementioned waterborne polyester resin (C) is preferably in the range of about 3,000 to 40,000, more preferably 10,000 to 30,000. When the weight-average molecular weight is 3,000 or higher, the abrasion resistance of the coating film becomes good, and when the weight-average molecular weight is 40,000 or lower, the flowability becomes good and the printability is improved.

[0104] Specific examples of waterborne polyester resins (C) include PLAS COAT Z-446, Z-561, Z-565, Z-880, Z-3310, RZ-105, RZ-570, Z-730, Z-760 (manufactured by Koyo Chemical Industry Co., Ltd.), ARON MELT PES-2155A30, 2255A30, 2500A30, 2655A30, 2405A30, 2353A25 (manufactured by Toa Synthetic Co., Ltd.).

[0105] The glass transition temperature (Tg) of the aforementioned adhesive resin is preferably -20 to 100°C. This is because it improves abrasion resistance and flexural strength. More preferably, it is -10 to 90°C, and even more preferably, it is 0 to 80°C. Here, the glass transition temperature (Tg) refers to the value measured based on JIS K0129. The value can be measured using differential scanning calorimetry (DSC), and the measuring instrument can be a Rigaku DSC8231.

[0106] <Body pigments>

[0107] The waterborne primer composition of the present invention comprises extender pigments. By including extender pigments, the rheology can be adjusted to a viscosity range suitable for flexographic and gravure printing, and the surface tension of the waterborne primer composition and the surface free energy of the primer layer formed by the waterborne primer composition can be adjusted. Examples of extender pigments used in the present invention include silica, calcium carbonate, barium sulfate, talc, magnesium carbonate, barium carbonate, calcium sulfate, kaolin, mica, calcium silicate, and aluminum silicate. From the viewpoint of rheological control such as viscosity, at least one of the group consisting of silica, calcium carbonate, barium sulfate, and talc is preferred, and silica is particularly preferred. This is because silica has silanol groups on its surface, resulting in a high surface free energy, which in turn increases the surface free energy of the primer layer itself. One extender pigment may be used alone, or two or more may be used in combination.

[0108] When using silica as an extender pigment, silica (hydrophobic silica) can be obtained by modifying and hydrophobizing the silanol groups on the silica surface with organosilicon compounds. The DBA (di-n-butylamine) value, which indicates the degree of hydrophobicity of the hydrophobic silica, is preferably 5 to 200, more preferably 20 to 175. Within this range, interaction with the dispersion resin is promoted, rheological adjustments are easier, and adjustments to reduce surface tension are easier. Furthermore, the lower the DBA value, the more the silanol groups are modified with organosilicon compounds, meaning a higher degree of hydrophobicity.

[0109] The content of the aforementioned extender pigment in the water-based primer composition is preferably in the range of 1 to 15% by mass, more preferably 2 to 12% by mass, and even more preferably 3 to 10% by mass. At 1% by mass or more, the gloss value can be reduced (giving a matte finish), and the surface free energy of the primer layer can be increased. Furthermore, by exposing the extender pigment on the surface, the unevenness allows for better ink adhesion and leveling of the active energy-cured composition. At 15% by mass or less, flowability and surface smoothness are improved, and abrasion resistance is good. Additionally, if within the above range, the transfer, ink adhesion, and leveling of the water-based primer composition on the paper substrate and / or ink layer, as well as the transfer, ink adhesion, and leveling of the active energy-cured composition on the primer layer, can be balanced. Therefore, the substrate adhesion and interlayer adhesion of the laminate are improved, and abrasion resistance is good.

[0110] The average particle size of the aforementioned extender pigments is preferably in the range of 1 to 10 μm, more preferably 2 to 8 μm, and even more preferably 2 to 5 μm. When the average particle size is 1 μm or more, the leveling properties of the active energy ray curing composition on the water-based primer are improved; when it is below 10 μm, the abrasion resistance is good, and a good matte finish can be obtained. Furthermore, to adjust the flow characteristics and control the size of surface unevenness, extender pigments with different average particle sizes can be used together. It should be noted that the aforementioned average particle size refers to the volume average particle size based on laser diffraction, which can be measured, for example, using a device such as the T330EXII manufactured by Macquarie Pharmaceuticals.

[0111] When using silica as an extender pigment, the average particle size is preferably in the range of 1 to 10 μm, more preferably 2 to 8 μm, and even more preferably 2 to 5 μm.

[0112] The specific surface area (m²) of the above-mentioned extender pigments based on the BET method 2 / g is preferably 50-500m 2 / g, more preferably 100-400m 2 / g, more preferably 100-350m 2 / g. In 50m 2 At g / g or higher, the matte finish is good, and at 500m 2 When the ratio is below / g, the fluidity of the primer composition can be maintained, thus the leveling becomes good.

[0113] When using silica as an extender pigment, the specific surface area m based on the BET method... 2 / g is preferably 50-500m 2 / g, more preferably 100-400m 2 / g, more preferably 100-350m 2 / g.

[0114] Specific examples of silica include MIZUKASIL P-705, P-707, P-709, P-78A, P-78D, P-78F, P-73, P-50 (manufactured by Mizusawa Chemical Industry Co., Ltd.), and Nipsil. E-74P, E75, E-743, E-150J, E-1030, E-200, E-170, E-220, E-200A, E-1009, E-220A, E-1011, N-300A, K-500, HD2, L-250, G-300 (manufactured by Tosoh Silica Co., Ltd.), SYLYSIA250, 250N, 256, 256N, 310P, 320, 350, 370, 380, 420, 430, 440, 450, 436, 446, 456, 530, 550, C-1504, C-1510, SYLOPHOBIC 100, 200, 702, 704, 4004, 507, 505, 603 (manufactured by Fuji SILYSIA Chemical Co., Ltd.), etc.

[0115] <Aqueous Solvents>

[0116] The aqueous primer composition of the present invention comprises an aqueous solvent. Water and / or a hydrophilic organic solvent are preferred as the aqueous solvent. In some embodiments, the aqueous solvent preferably comprises 20-90% by weight, more preferably 25-85% by weight, and particularly preferably 30-80% by weight, relative to the total weight of the aqueous primer composition. Furthermore, in some embodiments, the aqueous solvent preferably comprises 30-85% by weight, more preferably 40-80% by weight, and particularly preferably 50-75% by weight, relative to the total weight of the aqueous primer composition.

[0117] <Hydrophilic organic solvents>

[0118] This invention preferably includes a hydrophilic organic solvent. There are no particular limitations on the hydrophilic organic solvent as long as it is soluble in water; one type can be used alone, or two or more can be used in combination. The hydrophilic organic solvent refers to an organic solvent having hydrophilic groups such as ether groups and hydroxyl groups. The boiling point of the hydrophilic organic solvent is preferably 60–100°C, more preferably 70–90°C. By including a hydrophilic organic solvent with a boiling point above 60°C, the surface tension is reduced, thus improving the leveling of the water-based primer composition on paper substrates and ink layers. When the boiling point is below 100°C, since there is almost no residual hydrophilic organic solvent in the coating film during the drying process, the surface free energy of the primer layer itself is not reduced. Therefore, the ink adhesion and leveling of the active energy ray-cured composition are improved, thereby obtaining a good matte finish.

[0119] As a hydrophilic organic solvent, alcohol-based or ether-based organic solvents are preferred. Examples of alcohol-based organic solvents include methanol, ethanol, isopropanol, 2-butanol, diacetone alcohol, allyl alcohol, and 2-methyl-2-propanol, among which ethanol, methanol, isopropanol, and 2-butanol are preferred. Examples of ether-based organic solvents include n-propyl ether and ethylene glycol dimethyl ether, among which n-propyl ether is preferred.

[0120] The hydrophilic organic solvent preferably comprises 1 to 15% by mass, more preferably 2 to 10% by mass, relative to the total mass of the water-based primer composition. This is because the surface tension is reduced, thus improving the leveling of the water-based primer composition on paper substrates and / or ink layers. In addition, the hydrophilic organic solvent leaves almost no residual solvent in the coating film after thorough drying, therefore it does not reduce the surface free energy of the primer layer itself. The ink adhesion and leveling of the active energy ray-cured composition are improved, resulting in a good matte finish.

[0121] In some embodiments, the aqueous solvent preferably contains at least a hydrophilic organic solvent, and more preferably further contains water. When the aqueous solvent contains a hydrophilic organic solvent and water, the proportion of water to the total mass of the aqueous solvent is preferably 60-100% by mass, more preferably 70-100% by mass, and even more preferably 80-100% by mass. There are no particular limitations on the hydrophilic organic solvent used in conjunction with water, but alcohol-based organic solvents are preferred.

[0122] In some embodiments, the waterborne primer composition contains a binder resin, an extender pigment, and a hydrophilic organic solvent, and preferably contains only water as the hydrophilic organic solvent. In this embodiment, the binder resin may contain one or more of the resins described above. The combination of resins in the binder resin preferably includes an aqueous acrylic emulsion (A1) and a water-soluble acrylic resin (A2). That is, in some embodiments, the waterborne primer composition contains an aqueous acrylic emulsion (A1) and a water-soluble acrylic resin (A2), an extender pigment, and a hydrophilic organic solvent, and the hydrophilic organic solvent preferably contains only water.

[0123] (Curing agent)

[0124] In this invention, polyisocyanate-type curing agents may be appropriately added as needed, without hindering the purpose of this invention.

[0125] (additive)

[0126] In this invention, as needed, surface conditioners, leveling agents, wetting and penetrating agents, thickeners, anti-skinning agents, ultraviolet absorbers, antioxidants, crosslinking agents, preservatives, mildew inhibitors, viscosity modifiers, pH adjusters, and other additives may be appropriately added within the scope that does not impede the purpose of this invention.

[0127] (Surface Conditioner)

[0128] Furthermore, to ensure that the surface tension of the waterborne primer composition of the present invention is within a preferred range, a surface modifier may be incorporated within a range that does not impair the purpose of the present invention. Specific examples of surface modifiers include anionic surface modifiers such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts; nonionic surface modifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylenide glycols, polyoxyethylene-polyoxypropylene block copolymers, acetylenide glycols, and ethylene oxide addition-type acetylenide glycols; cationic surface modifiers such as alkylamine salts and quaternary ammonium salts; silicone-based surface modifiers; and fluorine-based surface modifiers. Among these, nonionic surface modifiers such as acetylenide glycols and ethylene oxide addition-type acetylenide glycols are preferred. It should be noted that the HLB (Hydrophile-Lipophile Balance) value of the surface modifier is not particularly limited as long as the waterborne primer composition has the desired surface tension; it is preferably 2 to 15, more preferably 3 to 10, and more preferably 4 to 9. A single surface conditioner can be used alone, or two or more can be used together.

[0129] Furthermore, the content of the surface modifier contained in the water-based primer of the present invention is appropriately selected according to its intended use. Generally speaking, it is preferably 0.01 to 10% by mass relative to the total mass of the water-based primer composition, and more preferably 0.5 to 8% by mass. By adjusting the amount of surface modifier added within the above range as needed, the surface of the water-based primer composition can be adjusted.

[0130] (Leveling agent)

[0131] In the aforementioned water-based primer layer, a leveling agent can be added to adjust surface properties (surface free energy, etc.) and improve coatability. For example, known leveling agents such as fluorinated, acrylic, siloxane-based agents and their adducts or mixtures can be used. The amount added can be appropriately determined, for example, based on the adjustment of surface properties and coatability.

[0132] (Viscosity of the primer composition)

[0133] In this invention, the viscosity of the water-based primer composition is preferably 50 to 2500 mPa·s, more preferably 100 to 1500 mPa·s, and particularly preferably 800 to 1500 mPa·s. When the viscosity is 50 Pa·s or higher, the transferability of the water-based primer composition to the paper substrate becomes good, and when the viscosity is 2500 Pa·s or lower, the leveling properties after ink application become good. Furthermore, the viscosity described herein is a measurement value based on the method described in JIS K5600-2, for example, a cone-plate viscometer can be used, measured at 25°C with a shear rate of 100 rpm, using a cone with a diameter of 35 mm and a cone angle of 1°.

[0134] In this invention, to ensure the viscosity of the water-based primer is within a preferred range, the content of extender pigment in the water-based primer is preferably set to 1-15% by mass, more preferably 2-10% by mass, and even more preferably 3-8% by mass. The content of hydrophilic organic solvent in the water-based primer is preferably 1-15% by mass, more preferably 2-10% by mass. The ratio of binder resin in the water-based primer is 10-50% by mass, more preferably 20-40% by mass.

[0135] (Thickener)

[0136] To ensure that the viscosity of the above-mentioned water-based primer composition is within a preferred range, a thickener may be included within the range that allows the effects of the present invention to be achieved. By including a thickener in the primer composition, the viscosity can be easily adjusted to correspond to the coating method. Examples of such thickeners include urethane-based thickeners and polyethylene oxide-based thickeners. Specific examples of urethane-based thickeners include ADEKA's ADEKANol UH-756VF, UH-752, and UH-472; Kusunoki Chemical's DISPARLON AQ-580, AQ-600, and AQ-607; and BYK-420. Specific examples of polyethylene oxide-based thickeners include Sumitomo Seika's PEO-1, PEO-2, and PEO-3; and Union Carbide's POLYOX N-80 and N-750. They can be used individually or in combination with two or more.

[0137] In the total mass of the water-based primer composition, the content of thickener is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 8.0% by mass, and particularly preferably 0.5 to 5.0% by mass. If the content of thickener is 0.1% by mass or more, the viscosity of the primer composition will not become too low, the extender pigments in the system will not easily settle, and the storage stability will be improved. In addition, if the content of thickener is 10.0% by mass or less, the viscosity of the primer composition will not become too high, and uneven thickness caused by uneven coating and poor leveling will not easily occur. It should be noted that when using a water-soluble thickener, the content of thickener refers to the converted content of solid components in the thickener.

[0138] <Manufacturing of Water-Based Primers>

[0139] As a method for manufacturing the water-based primer of the present invention, examples include mixing an adhesive resin, extender pigment, aqueous solvent, and pigments, curing agents, and additives as needed in necessary amounts, and then thoroughly mixing them with a mixer or the like, or dispersing them using a sand mill or the like.

[0140] <Active Energy Ray Curing Layer>

[0141] In the laminated packaging material of the present invention, the active energy ray-cured layer is formed from a cured product of an active energy ray-curable composition. Specifically, it is formed by printing an active energy ray-curable composition onto a primer layer and irradiating the resulting printed layer with active energy rays, thereby curing the composition constituting the printed layer. The specular gloss at 60° of the active energy ray-cured layer is preferably 40 or less, exhibiting excellent matting properties. More preferably, it is 18 or less, and even more preferably, it is 11 or less. The gloss value is measured using micro-TRI-gloss at an incident angle of 60°.

[0142] <Active Energy Ray Curing Composition>

[0143] As the active energy ray composition of the present invention, it is not particularly limited as long as it contains a compound that can be cured by active energy rays. From the viewpoint of abrasion resistance and matting properties, it is preferable to contain resin microparticles. In addition, as a preferred composition of the active energy ray curable composition, a composition containing polyfunctional urethane acrylate, a monofunctional vinyl unsaturated monomer, a difunctional vinyl unsaturated monomer, resin microparticles and a photopolymerization initiator can be exemplified.

[0144] <Preparation of Active Energy Ray Curable Compositions>

[0145] As a method for manufacturing active energy ray-cured compositions, polyfunctional urethane acrylate, monofunctional vinyl unsaturated monomers, difunctional vinyl unsaturated monomers, resin microparticles, and photopolymerization initiators can be produced by stirring in a paddle mixer (dispersant) for approximately 30 minutes to 3 hours. It should be noted that in cases where mixing is difficult or viscosity easily becomes uneven, roller mills, ball mills, pebble mills, grinding mills, sand mills, etc., can be used.

[0146] <Resin Microparticles>

[0147] In this invention, the resin microparticles perform the functions of abrasion resistance and matting properties. The average particle size of these resin microparticles is preferably 1–10 μm, more preferably 1.5–8 μm, even more preferably 2–6 μm, and particularly preferably 2–3 μm. The average particle size referred to here is the volume average particle size based on laser diffraction, which can be measured, for example, using a device such as the T330EXII manufactured by Macquarie Pharmaceuticals. In the total mass of the active energy radiation curable composition, the resin microparticles preferably comprise 5–40% by mass, more preferably 10–35% by mass, and even more preferably 20–30% by mass.

[0148] Preferred examples of resin microparticles include urethane resin microparticles, silicone resin microparticles, melamine resin microparticles, melamine-benzoguanamine resin microparticles, acrylic resin microparticles (e.g., polymethyl methacrylate resin microparticles), acrylic-styrene copolymer resin microparticles, polycarbonate resin microparticles, polyethylene resin microparticles, polystyrene resin microparticles, and benzoguanamine resin microparticles. These can be used alone or in combination of two or more. Uramate resin microparticles are more preferred. Two or more of the above-mentioned resin microparticles can be used in combination as needed.

[0149] Specific examples of urethane resin microparticles include cross-linked 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, and ART PEARL P-400T (manufactured by Negami Kogyo Co., Ltd.).

[0150] Specific examples of silicone resin microparticles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TREFIL E-506S, and EP-9215 (manufactured by Toray Industries, Inc.).

[0151] Specific examples of melamine resin microparticles include EPOSTAR SS, EPOSTAR S, EPOSTAR FS, EPOSTAR S6, and EPOSTAR S12 (manufactured by Nippon Shokubai Co., Ltd.). Specific examples of melamine-benzoguanamine resin microparticles include EPOSTAR M30 (manufactured by Nippon Shokubai Co., Ltd.).

[0152] Specific examples of acrylic resin microparticles include EPOSTAR MA1002, EPOSTAR MA1004, EPOSTAR MA1006, EPOSTAR MA1010 (manufactured by Nippon Shokubai Co., Ltd.), TAFTIC FH-S005, TAFTIC FH-S008, TAFTIC FH-S010, TAFTIC FH-S015, TAFTIC FH-S020 (manufactured by Toyobo Co., Ltd.), Chemisnow MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, and MX-3000 (manufactured by Soken Chemical Co., Ltd.).

[0153] Specific examples of acrylic-styrene copolymer resin microparticles include EPOSTAR MA2003 (manufactured by Nippon Shokubai Co., Ltd.), FS-102, FS-201, FS-301, MG-451, MG-351 (manufactured by Paint Industrial Coatings Co., Ltd.), etc.

[0154] Specific examples of polycarbonate resin microparticles include the microparticles described in Japanese Patent Application Publication No. 2014-125495, microparticles obtained by the manufacturing method described in Japanese Patent Application Publication No. 2011-26471, and microparticles obtained by the method described in Japanese Patent Application Publication No. 2001-213970.

[0155] Specific examples of polyethylene resin microparticles include MIPELON XM-220, XM221U (manufactured by Mitsui Chemicals Co., Ltd.), and FLO-BEADS LE-1080 (manufactured by Sumitomo Seika Co., Ltd.).

[0156] Specific examples of polystyrene microparticles include Chemisnow SX-130H, SX-350H, and SX-500H (manufactured by Soken Chemical Co., Ltd.).

[0157] Specific examples of benzoguanamine resin microparticles include EPOSTAR MS, EPOSTAR M05, and EPOSTAR L15 (manufactured by Nippon Shokubai Co., Ltd.).

[0158] <Paper substrate>

[0159] The paper substrate used in this invention is not particularly limited, but ordinary paper, corrugated paper, etc., are preferred. The film thickness is not specifically specified, but a paper substrate of 0.2 mm to 1.0 mm is preferred. The printing surface may also be corona treated. Furthermore, to allow for design flexibility, the paper substrate may be vapor-deposited with metals such as aluminum, or further surface treatments such as corona treatment may be performed. For example, thick coated paper and Mary Kote paper are preferred.

[0160] <Printing Ink Composition>

[0161] The aforementioned printing ink compositions may include, for example, known offset printing ink compositions, UV-curable offset printing inks, gravure ink compositions, flexographic ink compositions, UV-curable flexographic ink compositions, and other ink compositions; any printing ink composition may be used. Offset printing ink compositions and UV-curable offset printing inks are preferred because they have a wide color gamut and are easy to increase printing density, thus enabling the formation of printing ink layers with high color reproducibility and design flexibility. The printing ink compositions may be organic solvent-based, solvent-free, or water-based.

[0162] <Printing of Ink Layers>

[0163] As a printing method for the printing ink composition, known methods can be used. Examples include offset printing, flexographic printing, gravure printing, and screen printing, with offset printing being preferred. The thickness of the ink layer is preferably 0.1 to 15 μm, more preferably 0.5 to 12 μm. Furthermore, the ink layer can be formed by combining the above-mentioned printing ink composition, or it can be formed by drying or UV curing after printing.

[0164] Printing of Water-Based Primer Layers

[0165] In this invention, it is preferable to form a primer layer using the water-based primer of this invention on a substrate by printing. As a printing method for printing the water-based primer on the substrate, known methods can be used, with flexographic printing and gravure printing being preferred.

[0166] <Fabrication of Layered Structures>

[0167] The method for manufacturing the laminate of the present invention can be exemplified by forming a primer layer on a paper substrate by flexographic or gravure printing, then printing an active energy ray curing composition on the primer layer, and finally irradiating it with active energy rays to form an active energy ray curing layer. Alternatively, an example can be provided: after forming a printing layer of a printing ink composition on a paper substrate using a known printing method, forming a primer layer from an aqueous primer composition by flexographic or gravure printing, then printing an active energy ray curing composition on the primer layer, and finally irradiating it with active energy rays to form an active energy ray curing layer.

[0168] It should be noted that there are no particular limitations on the printing and coating methods of the active energy ray curable composition. For example, wet coating methods such as spraying, rinsing, dipping, flow coating, gravure printing, flexographic printing, roller coating, spin coating, dispenser, inkjet printing, and screen printing can be used. Among these, gravure printing and flexographic printing are preferred.

[0169] Examples of active energy rays include far-ultraviolet, ultraviolet, and near-ultraviolet rays. On the other hand, electron beams and proton beams can also be used. In this case, curing can be achieved even without the use of a photopolymerization initiator. However, considering factors such as curing speed, ease of obtaining the irradiation device, and price, the effect of ultraviolet irradiation is preferred.

[0170] As a method of curing by ultraviolet irradiation, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc., which emit light in the wavelength range of 150–450 nm are used, with a cumulative light intensity of 30–5000 mJ / cm². 2 Preferably 100~1000mJ / cm 2 That's it. After being exposed to ultraviolet light, it can also be heated as needed to achieve complete curing.

[0171] Example

[0172] The present invention will be specifically described below as an example, but the present invention is not limited to the following examples. In the present invention, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0173] (Surface tension)

[0174] Surface tension refers to surface tension based on the Wilhelmy method, for example, measured using a high-precision surface tension meter DY-700 (manufactured by Kyowa Interface Chemicals Co., Ltd.). It should be noted that the liquid temperature during measurement is set to 25°C.

[0175] (Surface free energy)

[0176] The surface free energy was measured using a fully automated contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd. The method was as follows: 1 μL of water (pure water) was dropped onto the primer surface, and the contact angle was measured after 30 seconds. Then, 1 μL of n-hexadecane was dropped onto the primer surface, and the contact angle was measured after 30 seconds. The values ​​were calculated using the obtained contact angles of the water and n-hexadecane through the Kaelble-Uy method.

[0177] (Average particle size)

[0178] The average particle size refers to the volume average particle size obtained by laser diffraction, measured using a T330EXII manufactured by Macquarie-Baier.

[0179] (Viscosity)

[0180] Viscosity was measured using the method described in JIS K5600-2, with a cone-plate viscometer at 25°C and a shear rate of 100 rpm. The cone-plate viscometer used a cone with a diameter of 35 mm and a cone angle of 1°.

[0181] (Glass transition temperature)

[0182] The glass transition temperature (Tg) was determined according to the method described in JIS K0129. Specifically, it was determined using a DSC (Differential Scanning Calorimeter). It should be noted that a Rigaku DSC8231 was used, with the measurement temperature range being -70 to 150°C, a heating rate of 10°C / min, and the midpoint between the endothermic onset and termination temperatures based on the glass transition in the DSC curve being taken as the glass transition temperature.

[0183] (Manufacturing Example 1: Preparation of Active Energy Ray Curing Composition U1)

[0184] 12 parts of urethane acrylate (BEAMSET 550B, manufactured by Arakawa Chemical Industry Co., Ltd.), 47 parts of 4-HBA (4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 25 parts of ART PEARL MM120T (urethane microparticles, average particle size 2 μm, glass transition temperature (Tg) 22℃, manufactured by Negami Kogyo Co., Ltd.), 4 parts of Omnirad TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide, manufactured by IGM Corporation) as a photopolymerization initiator, and 12 parts of silicone defoamer as an additive were mixed and stirred for 90 minutes using a paddle mixer to obtain active energy ray curing composition U1.

[0185] (Manufacturing Example 2: Preparation of Active Energy Ray Curing Composition U2)

[0186] 10 parts of urethane acrylate (BEAMSET 550B, manufactured by Arakawa Chemical Industry Co., Ltd.), 39 parts of 4-HBA (4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 35 parts of ART PEARL MM120T (urethane microparticles, average particle size 2 μm, glass transition temperature (Tg) 22 °C, manufactured by Negami Kogyo Co., Ltd.), 4 parts of Omnirad TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide, manufactured by IGM Corporation) as a photopolymerization initiator, and 12 parts of silicone defoamer as an additive were mixed and stirred for 90 minutes using a paddle mixer to obtain active energy ray curing composition U2.

[0187] (Manufacturing Example 3: Preparation of Active Energy Ray Curing Composition U3)

[0188] 21 parts of urethane acrylate (BEAMSET 550B, manufactured by Arakawa Chemical Industry Co., Ltd.), 57 parts of 4-HBA (4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 6 parts of ART PEARL MM120T (urethane microparticles, average particle size 2 μm, glass transition temperature (Tg) 22℃, manufactured by Negami Kogyo Co., Ltd.), 4 parts of Omnirad TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide, manufactured by IGM Corporation) as a photopolymerization initiator, and 12 parts of silicone defoamer as an additive were mixed and stirred for 90 minutes using a paddle mixer to obtain active energy ray curing composition U3.

[0189] (Example 1: Preparation of water-based primer composition S1)

[0190] 80 parts of waterborne acrylic emulsion (A1) (styrene-acrylic emulsion 1, Tg 25℃, solid content 40%), 5 parts of silica-1 (average particle size 3μm, oil absorption 260ml / 100g), 5 parts of ethanol, 8 parts of water, 2 parts of dispersant (BYK193) as an additive, and 2 parts of surface conditioner (TEGO Foamex 810, organosilicon) were mixed and stirred for 20 minutes using a paddle mixer to obtain waterborne primer composition S1.

[0191] (Examples 2-21, Comparative Examples 1-2: Preparation of water-based primer compositions S2-S21, T1-T2)

[0192] Except for changes to the raw materials and formulations recorded in Tables 1 and 2, water-based primers S2 to S21 and T1 to T2 were obtained using the same method as in Example 1. In the tables, values ​​without unit markings represent parts, and empty columns indicate no formulation.

[0193] Additionally, the abbreviations in the table indicate that the solvent for the adhesive resin is water.

[0194] Water-soluble acrylic resin (A2): Tg 19℃, solids content 25%;

[0195] Waterborne urethane resin (B1): Tg 25℃, solids content 30%;

[0196] Polyester resin (C): Tg 20℃, solids content 25%;

[0197] Styrene-butadiene resin: Tg 26℃, solids content 43%;

[0198] Silica-2: Average particle size 0.5 μm;

[0199] Silica-3: Average particle size 6μm, oil absorption 250ml / 100g;

[0200] Silica-4: Average particle size 12μm, oil absorption 240ml / 100g;

[0201] Silica-5: Average particle size 3.9μm, oil absorption 230ml / 100g, DBA value 50;

[0202] Calcium carbonate: average particle size 3μm, oil absorption 20ml / 100g;

[0203] Precipitating barium sulfate: average particle size 3 μm;

[0204] Clay: average particle size 3μm, oil absorption 51ml / 100g;

[0205] Methanol: Boiling point 64.7℃;

[0206] Isopropanol: Boiling point 82.3℃;

[0207] 2-Butanol: boiling point 100°C.

[0208] [Table 1]

[0209]

[0210] [Table 2]

[0211]

[0212] (Example 22: Fabrication of laminate T1)

[0213] First, on AURORACOAT (high-gloss coated paper, 81 μm thick, manufactured by Nippon Paper Corporation) as the paper substrate, on the upper half of the printing direction of the paper substrate, "FD CARTON X Ink M (manufactured by Toyo Ink Co., Ltd., containing polyfunctional (meth)acrylic monomers with more than three functions)" as a UV-curable offset printing ink was printed at an ink concentration of 1.75 (measuring device: X-Rite eXact (manufactured by X-Rite Corporation), conditions: illumination D50, standard observer 2°, concentration state E, no filter). Then, it was cured with a UV lamp. This allows for the production of prints with both areas of the paper substrate without an ink layer and areas with an ink layer. It should be noted that the printing speed was 8000 sheets / hour, and the UV lamps consisted of two air-cooled metal halide lamps and one high-pressure mercury lamp, with a total UV lamp intensity of 160 W / cm² (cumulative luminous intensity 450 mJ / cm²). 2 Then, on the printed material of the FD CARTON X ink M obtained above, the water-based primer S1 of Example 1 was coated using the flexographic coating unit of the sheet-fed printing press "LITHRONE26 (manufactured by Komori Corporation)" and dried using far-infrared light and a hot air dryer. The anilox roller used as the coating unit had a triple-helix engraving pattern, a line count of 80 lines / inch, and a unit volume of 15 ml / m³. 2 An anilox roller was then used. Next, on the printed material obtained above, the active energy ray curing composition U1 obtained in Manufacturing Example 1 was coated using the flexographic coating unit of a sheet-fed printing press "LITHRONE 26 (manufactured by Komori Corporation)" in the same manner as the water-based primer composition, and then cured with a UV lamp to obtain a laminate T1. It should be noted that the anilox roller used as the coating unit had a triple helix engraving pattern, a line count of 90 lines / inch, and a unit volume of 25 ml / m². 2 The anilox roller is used. Furthermore, during flexographic coating, the temperature is controlled at a printing speed of 8000 sheets / hour and a liquid temperature of 25°C for S1. Additionally, the type, number, and intensity of the UV lamps are the same as the curing conditions for the aforementioned FD CARTON X ink M.

[0214] (Examples 23-44, Comparative Examples 3-4: Fabrication of laminates L2-L23 and M1-2)

[0215] Using the same method as in Example 22, and under the configuration conditions shown in Tables 3 and 4, the water-based primers S2 to S21 obtained in Examples 2 to 21 and the active energy ray curing compositions U2 and U3 obtained in Manufacturing Examples 2 and 3 were used to obtain laminates L2 to L23 and M1 to 2.

[0216] [Table 3]

[0217]

[0218] [Table 4]

[0219]

[0220] (evaluate)

[0221] The following evaluation was conducted using a laminate of packaging material having the water-based primer composition and the active energy ray curing composition obtained in the above examples and comparative examples in sequence. The evaluation results are shown in Tables 3 and 4.

[0222] <Stain resistance>

[0223] For the laminates obtained in the examples and comparative examples, gloss values ​​were randomly measured at 50 locations on the water-based primer / active energy ray-cured layer on the FD CARTON X ink M ink layer and on the water-based primer / active energy ray-cured layer directly laminated on the paper substrate without the FD CARTON X ink M ink layer. The relative standard deviation of the gloss value (the proportion of the deviation relative to the average gloss value) was evaluated. A larger relative standard deviation indicates higher gloss unevenness, which is considered a deterioration in print appearance (color spots). Gloss values ​​were measured using BYK's micro-TRI-gloss at an incident angle of 60°. The evaluation criteria are as follows.

[0224] 5 (Excellent): Less than 2%

[0225] 4 (Good): 2% or more but less than 3%

[0226] 3 (optional): 3% or more but less than 5%

[0227] 2 (Not allowed): 5% or more but less than 10%

[0228] 1 (poor): more than 10%

[0229] In addition, its practical usability is rated as 3, 4 and 5.

[0230] <Extinction>

[0231] For the laminates obtained in the examples and comparative examples, the gloss value of the water-based primer / active energy ray cured layer directly laminated on the paper substrate, without the ink layer printed with FD CARTON X ink M, was measured. The gloss value was measured using a BYK micro-TRI-gloss at an incident angle of 60°. The evaluation criteria are as follows.

[0232] 5 (Excellent): 11 and below

[0233] 4 (Good): Gloss value greater than 11 and less than 18

[0234] 3 (Can be: gloss value greater than 18 and less than 40)

[0235] 2 (Not allowed): Gloss value greater than 40 and less than 50

[0236] 1 (Poor): Gloss value greater than 50

[0237] In addition, its practical usability is rated as 3, 4 and 5.

[0238] <Abrasion Resistance>

[0239] For the laminates obtained in the examples and comparative examples, the cured layers of the FD CARTON X ink M ink layer and the water-based primer / active energy X-ray curing layer were placed in contact with each other in a Sutherland Type Ink Rub Tester (manufactured by Toyo Seiki Co., Ltd.). After applying a 2-pound load for a specified number of cycles, the abrasion resistance was evaluated by visually confirming whether the cured layer had peeled off to reveal the substrate. The evaluation criteria are as follows.

[0240] 5 (Excellent): Even after 10,000 cycles, the cured layer does not peel off and the substrate is not visible.

[0241] 4 (Good): The cured layer peels off after 10,000 cycles, revealing the substrate, but the substrate is not visible after 9,000 cycles.

[0242] 3 (optional): The cured layer peels off after 9000 cycles, revealing the substrate, but the substrate is not visible after 8000 cycles.

[0243] 2 (Not allowed): The cured layer peels off after 8000 cycles, revealing the substrate, but the substrate is not visible after 7000 cycles.

[0244] 1 (Poor): Even after 7000 cycles, the cured layer peels off, exposing the substrate.

[0245] In addition, its practical usability is rated as 3, 4 and 5.

[0246] As can be seen from Tables 3 and 4, according to the present invention, a water-based primer composition with excellent resistance to staining (resistance to uneven gloss) when coated on an active energy ray curing composition, as well as a laminate for packaging materials with excellent cosmetic appearance (matte finish) and abrasion resistance, can be provided.

[0247] Comparative Examples 1 and 2, which do not contain extender pigments, have poor resistance to staining and matting.

Claims

1. A water-based primer composition, characterized in that, The aqueous primer composition is used to form the primer layer of a laminate for packaging materials having sequentially a paper substrate, a primer layer, and an active energy radiation-curable layer containing resin particles. The aqueous primer composition comprises a binder resin, extender pigments, and an aqueous solvent. The body pigment contains at least one selected from the group consisting of silicon dioxide, calcium carbonate, barium sulfate, and talc. The average particle size of the extender pigment is 2~5μm. The content of the extender pigment in the water-based primer composition is 1-15% by mass. The adhesive resin comprises at least one selected from the group consisting of waterborne acrylic resin (A), waterborne urethane resin (B), and waterborne polyester resin (C). The glass transition temperature (Tg) of the adhesive resin is 0~100℃.

2. The water-based primer composition according to claim 1, characterized in that, The surface tension of the water-based primer composition is 24~38 mN / m.

3. The water-based primer composition according to claim 1 or 2, characterized in that, The surface free energy of the primer layer is 24~40 dyne / cm.

4. The water-based primer composition according to claim 1 or 2, characterized in that, The aqueous solvent includes hydrophilic organic solvents.

5. The water-based primer composition according to claim 1 or 2, characterized in that, The viscosity of the water-based primer composition is 50~2500 mPa·s.

6. The water-based primer composition according to claim 4, characterized in that, The boiling point of the hydrophilic organic solvent is 70~90℃.

7. The water-based primer composition according to claim 1 or 2, characterized in that, The water-based primer composition is used for flexographic or gravure printing.

8. A laminated body for packaging materials, characterized in that, The packaging material laminate sequentially comprises a paper substrate, a primer layer formed by the water-based primer composition according to any one of claims 1 to 7, and an active energy ray curing layer, wherein the water-based primer composition comprises an adhesive resin, an extender pigment, and an aqueous solvent, and the active energy ray curing layer comprises resin particles.

9. The laminated body for packaging materials according to claim 8, characterized in that, The packaging material laminate further includes an offset printing layer.

10. The laminated body for packaging materials according to claim 8, characterized in that, The gloss level of the active energy ray-cured layer at 60° is below 40.

11. A method for manufacturing a laminated body for packaging materials, characterized in that, The packaging material laminate sequentially comprises a paper substrate, a primer layer formed from the aqueous primer composition according to any one of claims 1 to 7, and an active energy radiation curing layer, wherein the method for manufacturing the packaging material laminate includes: The process of forming a primer layer on a paper substrate by flexographic or gravure printing of an aqueous primer composition comprising an adhesive resin, extender pigment, and an aqueous solvent; and The process of forming a cured layer of the active energy ray curable composition by irradiating it with active energy rays after printing an active energy ray curable composition containing resin particles onto the primer layer.

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