JP2023178658A - Aqueous varnish composition, kit, article with printed layer, and production method thereof - Google Patents

Abstract

To provide an aqueous varnish composition from which a printed layer excellent in transparency, and whitening resistance and scratch resistance after contraction can be formed, a kit, an article with the printed layer and a production method thereof.SOLUTION: An aqueous varnish composition contains an aqueous binder resin (A), a large particle size wax (B) having an average particle size of 1 to 8 μm, a small particle size wax (C) having an average particle size of 0.005 to 0.3 μm, a silicone additive (D), and an aqueous medium (E). The aqueous varnish composition for use contains 5 mass% or less of the large particle size wax (B) relative to the total mass of non-volatile components of the aqueous varnish composition.SELECTED DRAWING: None

Description

The present invention relates to an aqueous varnish composition, a kit, an article with a printed layer, and a method for producing the same.

BACKGROUND ART Plastic containers, metal containers, paper containers, etc. are used as packaging containers for beverages, foods such as side dishes and boxed lunches, and daily necessities such as cosmetics. Plastic labels are often attached to these packaging containers. As a plastic label, it can follow the shape of the packaging container and easily fit into the packaging container, so it is possible to print on the second side, which is the back side of the heat-shrinkable film (shrink film), which shrinks when heated. Shrink labels are used that are provided with a printed layer (hereinafter also referred to as a "picture layer") formed using an ink composition for the purpose of imparting functionality and the like.
Further, a varnish composition is printed on the surface of the heat-shrinkable film for the purpose of surface protection, etc., and a printed layer may also be provided on the first surface of the heat-shrinkable film.

Conventionally, organic solvent-based ink compositions and varnish compositions have been used, but water-based ink compositions and varnish compositions are being promoted from the viewpoint of reducing environmental impact.
For example, Patent Document 1 discloses a shrink label in which a printing layer formed using water-based ink is provided on the back side of a heat-shrinkable film.

Japanese Patent Application Publication No. 2001-215880

By the way, varnish compositions used for manufacturing shrink labels usually contain wax for the purpose of imparting scratch resistance to the printed layer formed. As the wax content increases, the scratch resistance of the printed layer tends to increase, but the transparency of the varnish composition also tends to decrease.
For shrink labels, the heat-shrinkable film shrinks when heat is applied, but the printed layer formed using a varnish composition on the surface (first side) of the heat-shrinkable film has the same shrinkability as the heat-shrinkable film. Not yet. Therefore, when the heat-shrinkable film shrinks, fine cracks may occur in the printed layer, and the printed layer may appear whitened. As mentioned above, as the content of wax in the varnish composition increases, the transparency of the varnish composition decreases, so the transparency of the printed layer before shrinkage also decreases, and the printed layer after shrinkage is more likely to whiten. (decreased resistance to whitening after shrinkage). If the transparency of the printed layer before shrinkage decreases or the whitening resistance of the printed layer after shrinkage decreases, the print layer (picture layer) provided on the back side (second side) of the heat-shrinkable film will deteriorate. Visibility will decrease.
If the content of wax in the varnish composition is reduced, it is possible to suppress a decrease in the transparency of the printed layer and the resistance to whitening after shrinkage, but it becomes difficult to obtain sufficient scratch resistance.

As described above, it is difficult to achieve both transparency and whitening resistance of the printed layer formed on the surface (first surface) of the heat-shrinkable film, and scratch resistance.
The water-based ink described in Patent Document 1 forms a pattern layer on the back surface (second surface) of a heat-shrinkable film, and has both transparency, resistance to whitening after shrinkage, and scratch resistance. An aqueous varnish composition capable of forming a printed layer is not yet known.

An object of the present invention is to provide an excellent aqueous varnish composition, a kit, an article with a printed layer, and a method for producing the same, which can form a printed layer with excellent transparency, post-shrinkage whitening resistance, and scratch resistance.

The present invention has the following aspects.
[1] Water-based binder resin (A), large particle wax (B) with an average particle diameter of 1 to 8 μm, small particle wax (C) with an average particle diameter of 0.005 to 0.3 μm, and silicone An aqueous varnish composition containing a system additive (D) and an aqueous medium (E),
An aqueous varnish composition in which the content of the large particle size wax (B) is 5% by mass or less based on the total mass of nonvolatile components of the aqueous varnish composition.
[2] The aqueous varnish composition of [1] above, wherein the mass ratio expressed by the large particle wax (B)/the small particle wax (C) is from 0.1 to 10.
[3] The total content of the large particle wax (B) and the small particle wax (C) is 0.5 to 8% by mass based on the total nonvolatile content of the aqueous varnish composition. , the aqueous varnish composition of [1] or [2] above.
[4] Any one of [1] to [3] above, wherein the content of the silicone additive (D) is 0.1 to 5% by mass based on the total mass of nonvolatile components of the aqueous varnish composition. An aqueous varnish composition.
[5] The aqueous varnish composition according to any one of [1] to [4] above, wherein the silicone additive (D) contains polydimethylsiloxane.
[6] The aqueous varnish composition according to any one of [1] to [5], wherein the aqueous binder resin (A) contains at least one of an acrylic resin emulsion and an acrylic urethane resin emulsion.
[7] The aqueous varnish composition according to any one of [1] to [6], wherein at least one of the large particle size wax (B) and the small particle size wax (C) contains a polyolefin wax.
[8] The aqueous varnish composition according to any one of [1] to [7] above, which is used for flexographic printing.
[9] The aqueous varnish composition according to any one of [1] to [8] above, further comprising a curing agent (F).
[10] A kit containing independently the aqueous varnish composition according to any one of [1] to [8] and a curing agent (F).
[11] A first printed layer formed using the aqueous varnish composition according to any one of [1] to [9] or the kit according to [10] above is provided on the first surface of the plastic film. , an article with a printed layer.
[12] The article with a printed layer according to [11] above, wherein a second printed layer is provided on the second surface of the plastic film.
[13] The article with a printed layer according to [11] or [12] above, wherein the plastic film is a heat-shrinkable film.
[14] A step of forming a first printed layer on the first surface of the plastic film using the aqueous varnish composition according to any one of [1] to [9] above or the kit according to [10] above, A method for producing an article with a printed layer.
[15] The method for producing an article with a printed layer according to [14], further comprising the step of forming a second printed layer on the second surface of the plastic film.
[16] The method for producing an article with a printed layer according to [14] or [15] above, wherein the plastic film is a heat-shrinkable film.

According to the present invention, it is possible to provide an aqueous varnish composition, a kit, an article with a printed layer, and a method for manufacturing the same, which can form a printed layer with excellent transparency, post-shrinkage whitening resistance, and scratch resistance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of an article with a printed layer of the present invention.

The present invention will be explained in detail below. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention only to these embodiments. The present invention can be implemented in various ways without departing from the spirit thereof.
In the present invention, "aqueous" in the aqueous varnish composition means containing water as a medium.
"Water-based acrylic resin" is a general term for "water-soluble acrylic resin" and "water-dispersible acrylic resin (acrylic resin emulsion, acrylic resin dispersion)." The same applies to "aqueous acrylic urethane resin", "aqueous urethane resin", etc.
"Nonvolatile matter" refers to the components contained in the water-based varnish composition excluding volatile media such as water and organic solvents, and is the component that will ultimately form the printing layer. Specifically, it was measured in accordance with JIS K 5601-1-2:2008.
In this specification, "(meth)acrylate" is a general term for "acrylate" and "methacrylate.""(Meth)acrylicacid" is a general term for "acrylic acid" and "methacrylic acid."

[Aqueous varnish composition]
An aqueous varnish composition according to an embodiment of the present invention includes an aqueous binder resin (A) shown below, a large particle wax (B), a small particle wax (C), and a silicone additive (D). and an aqueous medium (E).
The aqueous varnish composition may optionally contain an aqueous binder resin (A), a large particle size wax (B), a small particle size wax (C), and a silicone additive, as long as the effects of the present invention are not impaired. It may further contain components (optional components) other than (D) and the aqueous medium (E).

<Aqueous binder resin (A)>
Examples of the aqueous binder resin (A) include aqueous acrylic resin, aqueous acrylic urethane resin, aqueous urethane resin, aqueous polyester resin, aqueous polyamide resin, aqueous salt-vinyl acetate copolymer resin, aqueous cellulose resin, aqueous epoxy resin, and aqueous olefin resin. can be mentioned. Among these, adhesion of a printed layer (hereinafter also referred to as "first printed layer" or "protective layer") formed using an aqueous varnish composition or a kit described below to a base material such as a plastic film. From the viewpoint of further improving the properties and scratch resistance, water-based acrylic resins, water-based acrylic urethane resins, and water-based urethane resins are preferred, water-based acrylic resins and water-based acrylic urethane resins are more preferred, and acrylic resin emulsions and acrylic urethane resin emulsions are even more preferred. , acrylic resin emulsions are particularly preferred.
These aqueous binder resins (A) may be used alone or in combination of two or more.

(water-based acrylic resin)
Aqueous acrylic resin is a resin containing (meth)acrylate units.
Examples of water-based acrylic resins include homopolymers of (meth)acrylates, copolymers of two or more types of (meth)acrylates, and copolymers of (meth)acrylates and monomers other than (meth)acrylates. It will be done.
The ratio of (meth)acrylate units to the total mass of all monomer units constituting the aqueous acrylic resin is preferably 10 to 100% by mass, more preferably 20 to 100% by mass.

Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and isobutyl (meth)acrylate. Alkyl (meth)acrylates such as meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate; phenyl (meth)acrylate; ) acrylate and other aryl (meth)acrylates; aralkyl (meth)acrylates such as benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Examples include hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate.
These (meth)acrylates may be used alone or in combination of two or more.

Examples of monomers other than (meth)acrylate include conjugated diene compounds such as 1,3-butadiene, isoprene, and chloroprene; aromatic vinyl compounds such as styrene, α-methylstyrene, halogenated styrene, and divinylbenzene; acrylonitrile; Vinyl cyanide compounds such as methacrylonitrile; Acrylamides such as N,N-dimethyl (meth)acrylamide and N,N-diethyl (meth)acrylamide; Saturated carboxylic acids; unsaturated carboxylic acid esters such as diethyl maleate, dibutyl maleate, dibutyl fumarate, diethyl itaconate, and dibutyl itaconate.
These monomers may be used alone or in combination of two or more.

The weight average molecular weight of the water-based acrylic resin is preferably 5,000 to 1,500,000, more preferably 10,000 to 1,200,000, and even more preferably 20,000 to 1,000,000. If the weight average molecular weight of the water-based acrylic resin is at least the above lower limit, the solvent resistance and blocking resistance of the first printing layer will improve, and if it is below the above upper limit, the first printing layer will adhere to the base material. Improves sex.

The weight average molecular weight of the aqueous acrylic resin is a weight average molecular weight in terms of standard polystyrene molecular weight, and is measured by gel permeation chromatography (GPC).

The glass transition temperature of the aqueous acrylic resin is preferably -10 to 80°C, more preferably 0 to 70°C, even more preferably 0 to 60°C. If the glass transition temperature of the water-based acrylic resin is equal to or higher than the above lower limit value, the scratch resistance of the first printing layer will be further improved, and in addition, the blocking resistance will be improved, and if it is below the above upper limit value, the first printing layer will be improved. The adhesion of the layer to the substrate is improved, as well as the resistance to whitening after shrinkage.
Hereinafter, in this specification, the aqueous acrylic resin having a glass transition temperature of -10 to 80°C is also referred to as "aqueous acrylic resin (a1)".

In addition, even if the water-based acrylic resin has a glass transition temperature exceeding 80°C (hereinafter also referred to as "water-based acrylic resin (a2)"), it can be resistant as long as it does not impair adhesion and resistance to whitening after shrinkage. For the purpose of improving blocking properties, it may be used in combination with the water-based acrylic resin (a1).
When the aqueous acrylic resin (a1) and the aqueous acrylic resin (a2) are used together, the blocking resistance tends to increase as the proportion of the aqueous acrylic resin (a2) increases. From the viewpoint of increasing blocking resistance, the mass ratio of the water-based acrylic resin (a1) to the mass of the water-based acrylic resin (a2), that is, the mass ratio expressed as water-based acrylic resin (a1)/water-based acrylic resin (a2) (hereinafter , also referred to as "a1/a2 ratio") is preferably 10 or less, more preferably 9 or less, even more preferably 8.5 or less, particularly preferably 8 or less, and most preferably 7.5 or less. On the other hand, from the viewpoint of maintaining good adhesion and whitening resistance after shrinkage, the a1/a2 ratio is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, and especially 1.5 or more. Preferably, 2 or more is most preferable.
The upper limit and lower limit of the a1/a2 ratio can be arbitrarily combined. For example, considering the balance between adhesion, whitening resistance after shrinkage, and blocking resistance, the a1/a2 ratio is preferably 0.5 to 10, more preferably 0.8 to 9, and 0.8 to 8.5. is more preferable, 0.8 to 8 is more preferable, 0.8 to 7.5 is even more preferable, 1 to 7.5 is even more preferable, 1.5 to 7.5 is particularly preferable, 2 to 7.5 is most preferred.

The glass transition temperature of the water-based acrylic resin is measured in accordance with JIS K 7121:2012 as follows.
From the intersection of the baseline and the tangent of the endothermic curve in the curve (DSC curve) obtained by heating 10 mg of aqueous acrylic resin from -100 ° C to 160 ° C at 20 ° C / min using a differential scanning calorimeter. Find the glass transition temperature.

The aqueous acrylic resin preferably has an acid value, preferably 10 to 300 mgKOH/g, more preferably 15 to 250 mgKOH/g. Good water solubility can be obtained because the water-based acrylic resin has an acid value. Furthermore, when a curing agent (F) described below is used in combination, a robust first printed layer can be obtained by crosslinking with the curing agent.

The acid value of water-based acrylic resin is the amount of potassium hydroxide required to neutralize acid groups such as carboxy groups per gram of sample non-volatile matter expressed in milligrams, and is based on JIS K 5601-2-1. :1999.

The water-based acrylic resin is obtained by polymerizing a monomer component containing (meth)acrylate and, if necessary, a monomer other than (meth)acrylate.
The polymerization method is not particularly limited, but examples include methods in which monomer components are polymerized by solution polymerization, bulk polymerization, emulsion polymerization, etc. in the presence of a known radical polymerization initiator.
The water-based acrylic resin may be of a self-crosslinking type.

As the water-based acrylic resin, commercially available products may be used. Commercially available products include, for example, products manufactured by Seiko PMC Co., Ltd. under the trade names "Hilos-X TE-1048", "Hilos-X NE-2186", "Hilos-X KE-1062", "Hilos-X QE-1042", "Hilos-X -1304", "Hilos-X KE-2536", "Hilos-X J-140A", "Hilos-X TE-1102", "Hilos-X RE-218", "Hilos-X NE-2009", " HILOS-X JE-1056'', ``HILOS-X KE-1148'', ``HILOS-X M-141'', ``HILOS-X ME-2039'', ``HILOS-X UE-1051'', ``HILOS-X PE- 1126'', ``Hilos-X JE-1113''; product names manufactured by Aica Kogyo Co., Ltd.: ``Ultrasol A-25'', ``Ultrasol A-35'', ``Ultrasol A-40'', ``Ultrasol A-50'' ”, “Ultrasol C-63”, “Ultrasol C-70”, “Ultrasol D-32”, “Ultrasol D-40”, “Ultrasol GP-300”, “Ultrasol UL-1097”; Product names manufactured by BASF Japan Co., Ltd.: "Jonkryl PDX-7357", "Jonkryl PDX-7182", "Jonkryl PDX-7326", "Jonkryl PDX-7616A", "Jonkryl PDX-7732", "Jonkryl PDX-7732" JONKRYL PDX-7741", "JONKRIL PDX-7787", "JONKRIL PDX-7356", "JONKRIL PDX-7734", "JONKRIL PDX-7777", "JONKRIL PDX-7615", "JONKRIL PDX -7775'', ``Jonkrill PDX-7692'', ``Jonkrill PDX-7630A'', ``Jonkrill PDX-7158'', ``Jonkrill 352D'', ``Jonkrill PDX-7199'', ``Jonkrill PDX-7358'', "Jonkrill PDX-7667", "Jonkrill PDX-7700", "Jonkrill PDX-7696", "Jonkrill PDX-7780", "Jonkrill PDX-7177", "Jonkrill PDX-7164", "Jonkrill ``Krill PDX-7430''.
These water-based acrylic resins may be used alone or in combination of two or more.

(Water-based acrylic urethane resin)
Examples of the water-based acrylic urethane resin include reaction products of polyvalent isocyanate compounds, polyol compounds, and hydroxy group-containing (meth)acrylates, or reaction products of polyvalent isocyanate compounds and hydroxy group-containing (meth)acrylates. It will be done.

Examples of the polyvalent isocyanate compound include aliphatic, alicyclic, aromatic, and other polyvalent isocyanate compounds. Specific examples of polyvalent isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3 -Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate; hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1 , 3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate) , methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane; m-phenylene Diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate , dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate and other aromatic diisocyanates; using the above diisocyanates, polymerized polyisocyanate compounds having allophanate structures, nurate structures, biuret structures, etc.; 1,3,5- Triisocyanates such as triisocyanate benzene, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate hexane; 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate, etc. Examples include polyisocyanates.
These polyvalent isocyanate compounds may be used alone or in combination of two or more.

Examples of polyol compounds include polyols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low molecular weight polyols such as ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as initiators. Ether polyol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, octanediol, 1,9-nonanediol, 1,8-nonanediol, 1,4- Saturated or unsaturated glycols such as cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid Polyester polyol obtained by dehydration condensation of dibasic acids such as , oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, or their corresponding acid anhydrides or dimer acids; polyethylene; Polyolefin polyols such as polyols and polypropylene polyols; polyether ester polyols obtained by reacting the dibasic acids or their dialkyl esters with the polyether polyols; the glycols and methyl carbonate, diphenyl carbonate, ethylene carbonate, Examples include polycarbonate polyols obtained by reacting with phosgene and the like.
These polyol compounds may be used alone or in combination of two or more.

Examples of the hydroxy group-containing (meth)acrylate include the hydroxyalkyl (meth)acrylates exemplified above in the description of the aqueous acrylic resin.
Further, as the aqueous acrylic urethane resin, for example, a core-shell type resin having an acrylic resin in the core portion and a urethane resin in the shell portion may be used.

The weight average molecular weight of the aqueous acrylic urethane resin is preferably 5,000 to 120,000, more preferably 10,000 to 100,000, and even more preferably 10,000 to 80,000. If the weight average molecular weight of the water-based acrylic urethane resin is at least the above lower limit, the solvent resistance and blocking resistance of the first printed layer will improve, and if it is below the above upper limit, the abrasion resistance of the first printed layer will improve. In addition, the adhesion to the substrate is improved.
The weight average molecular weight of the water-based acrylic urethane resin can be measured by the same method as the weight average molecular weight of the water-based acrylic resin.

The glass transition temperature of the aqueous acrylic urethane resin is preferably -30 to 100°C, more preferably -30 to 90°C, even more preferably -20 to 90°C. If the glass transition temperature of the aqueous acrylic urethane resin is equal to or higher than the above lower limit value, the scratch resistance of the first printing layer will be further improved, and in addition, the blocking resistance will be improved, and if it is below the above upper limit value, the first printing layer will be improved. The abrasion resistance of the printed layer is further improved, and in addition, the adhesion to the substrate is improved.
The glass transition temperature of the water-based acrylic urethane resin can be measured by the same method as the glass transition temperature of the water-based acrylic resin.

The aqueous acrylic urethane resin preferably has an acid value, preferably 1 to 100 mgKOH/g, more preferably 1 to 60 mgKOH/g. Good water solubility can be obtained because the water-based acrylic urethane resin has an acid value. Furthermore, when a curing agent (F) described below is used in combination, a robust first printed layer can be obtained by crosslinking with the curing agent.
The acid value of the water-based acrylic urethane resin can be measured by the same method as the acid value of the water-based acrylic resin.

The aqueous acrylic urethane resin is obtained by reacting a polyvalent isocyanate compound, a polyol compound, and a hydroxy group-containing (meth)acrylate, or a polyvalent isocyanate compound and a hydroxy group-containing (meth)acrylate by a known method.

As the water-based acrylic urethane resin, commercially available products may be used. Commercially available products include, for example, trade names "WEM-200U", "WEM-505C", and "WEM-3000" manufactured by Taisei Fine Chemical Co., Ltd.
One type of aqueous acrylic urethane resin may be used alone or two or more types may be used in combination.

(Water-based urethane resin)
Examples of the aqueous urethane resin include reaction products of polyvalent isocyanate compounds and polyol compounds. A polyvalent isocyanate compound is an organic compound having at least two isocyanate groups in one molecule. A polyol compound is an organic compound having at least two hydroxyl groups in one molecule.
Examples of the polyvalent isocyanate compound include the polyvalent isocyanate compounds exemplified above in the description of the aqueous acrylic urethane resin.
Examples of the polyol compound include the polyol compounds exemplified above in the description of the aqueous acrylic urethane resin.

The weight average molecular weight of the aqueous urethane resin is preferably from 3,000 to 100,000, more preferably from 7,000 to 90,000, even more preferably from 20,000 to 80,000. If the weight average molecular weight of the water-based urethane resin is at least the above lower limit, the blocking resistance of the first printed layer will be improved, and if it is below the above upper limit, the abrasion resistance of the first printed layer will be further improved, In addition, adhesion to the base material is improved.
The weight average molecular weight of the aqueous urethane resin can be measured by the same method as the weight average molecular weight of the aqueous acrylic resin.

The glass transition temperature of the aqueous urethane resin is preferably -10 to 130°C, more preferably 20 to 120°C, even more preferably 40 to 100°C. If the glass transition temperature of the aqueous urethane resin is equal to or higher than the above lower limit, the blocking resistance of the first printed layer will be improved, and if it is below the above upper limit, the scratch resistance of the first printed layer will be further improved, In addition, adhesion to the base material is improved.
The glass transition temperature of the water-based urethane resin can be measured by the same method as the glass transition temperature of the water-based acrylic resin.

The aqueous urethane resin preferably has an acid value, preferably 1 to 60 mgKOH/g, more preferably 1 to 50 mgKOH/g. Good water solubility can be obtained because the water-based urethane resin has an acid value. Furthermore, when a curing agent (F) described below is used in combination, a robust first printed layer can be obtained by crosslinking with the curing agent.
The acid value of the water-based urethane resin can be measured by the same method as the acid value of the water-based acrylic resin.

The water-based urethane resin can be obtained, for example, by reacting a polyvalent isocyanate compound and a polyol compound by a known method.
Alternatively, a silanol group may be introduced by reacting a hydrolyzable silicon group-containing compound with a reaction product of a polyvalent isocyanate compound and a polyol compound. In this specification, an aqueous urethane resin into which a silanol group is introduced is also referred to as a "silanol group-containing aqueous urethane resin."
The hydrolyzable silicon group-containing compound is a compound containing a hydrolyzable silicon group, and preferably further contains an active hydrogen group in addition to the hydrolyzable silicon group.
Examples of the hydrolyzable silicon group include groups in which a hydrolyzable group that is generated upon hydrolysis is bonded to a silicon group atom in the presence or absence of a silanol condensation catalyst. Examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Typically, one to three hydrolyzable groups are bonded to one silicon atom.
Examples of active hydrogen groups include amino groups, hydroxy groups, and mercapto groups.

As the water-based urethane resin, commercially available products may be used. Commercially available products include, for example, "Hydran WLS-210" manufactured by DIC Corporation; "Neo Sticker 400" and "Neo Sticker 200" manufactured by Nicca Chemical Co., Ltd.; and products manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Name: "Superflex 500M"; product names: "Takelac W-6010", "Takelac WS-5100", "Takelac WS-4000", and "Takelac W-635" manufactured by Mitsui Chemicals, Inc.
One type of aqueous urethane resin may be used alone or two or more types may be used in combination.

<Large particle diameter wax (B)>
The large particle diameter wax (B) is used to improve the scratch resistance of the first printed layer.
The large particle size wax (B) is a wax with an average particle size of 1 to 8 μm.
The average particle diameter of the large particle size wax (B) is 1 to 8 μm, preferably 2 to 6 μm. If the average particle diameter of the large particle diameter wax (B) is equal to or greater than the above lower limit value, the scratch resistance of the first printing layer will be improved, and if it is equal to or less than the above upper limit value, it will be used as a base material for an aqueous varnish composition during flexographic printing. The transferability to is improved.

The average particle diameter of the large particle size wax (B) is determined by measuring the volume-based particle size distribution using the Coulter counter method, and calculating the volume-based cumulative frequency 50% particle size (median diameter) from the obtained particle size distribution. :D50) and is also called the volume average particle diameter.
The Coulter counter method is to electrically measure the particle size and particle size distribution of wax particles dispersed in a solution by passing them through pores and observing changes in the electrical signal as the particles pass through. It's a method.

The large particle size wax (B) may have any shape as long as it is particulate, but it is preferably spherical, and more preferably true spherical. The closer the shape is to a perfect sphere, the more the scratch resistance of the first printed layer tends to improve.

Examples of the large particle size wax (B) include polyolefin wax (polyethylene wax, polypropylene wax, etc.), polytetrafluoroethylene wax, Fischer-Tropsch wax, amide wax, paraffin wax, microcrystalline wax, montan wax, carnauba wax, beeswax, etc. can be mentioned. Among these, polyolefin wax is preferred, and polyethylene wax is more preferred, from the viewpoint of improving wear resistance.
These large particle diameter waxes (B) may be used alone or in combination of two or more.

The softening point of the polyolefin wax is preferably 90 to 150°C, more preferably 100 to 140°C. If the softening point of the polyolefin wax is within the above range, wear resistance will be improved.
The softening point of polyolefin wax can be measured by the ring and ball method (JIS K 2207).

The large particle size wax (B) may be used in the form of a dispersion in water.
Furthermore, a commercially available product may be used as the large particle size wax (B). Commercially available products include, for example, those manufactured by Mitsui Chemicals Co., Ltd. under the trade names of "Chemipearl W100,""chemipearlW200,""chemipearlW300,""chemipearlW308,""chemipearlW400,""chemipearlW401,""chemipearlW500," and "chemipearl W300." Chemipearl W640, Chemipearl W700, Chemipearl W800; BYK product names: CERAFLOUR925, CERAFLOUR929, CERAFLOUR960, CERAFLOUR961, CERAFLOUR988, CERAFLOUR9 91", "CERAFLOUR994", "CERAFLOUR1000 ”; trade name “Jonkryl Wax 4” manufactured by BASF Japan is mentioned.

<Small particle size wax (C)>
The small particle size wax (C) is used to improve the transparency of the first printing layer and the resistance to whitening after shrinkage.
The small particle size wax (C) is a wax with an average particle size of 0.005 to 0.3 μm.
The average particle diameter of the small particle size wax (C) is 0.005 to 0.3 μm, preferably 0.01 to 0.2 μm. If the average particle diameter of the small particle size wax (C) is equal to or greater than the above lower limit value, the abrasion resistance will be improved, and if it is equal to or less than the above upper limit value, the transparency of the first printing layer and the resistance to whitening after shrinkage will be improved. do.
The average particle size of the small particle size wax (C) is determined by measuring the volume-based particle size distribution using a dynamic light scattering method, and calculating the volume-based particle size with a cumulative frequency of 50% from the obtained particle size distribution ( Median diameter: D50), also called volume average particle diameter.

The small particle size wax (C) may have any shape as long as it is particulate, but it is preferably spherical, and more preferably true spherical. The closer the shape is to a perfect sphere, the more the transparency of the first printed layer and the resistance to whitening after shrinkage tend to improve.

Examples of the small particle size wax (C) include polyolefin wax (polyethylene wax, polypropylene wax, etc.), polytetrafluoroethylene wax, Fischer-Tropsch wax, amide wax, paraffin wax, microcrystalline wax, montan wax, carnauba wax, beeswax, etc. can be mentioned. Among these, polyolefin wax is preferred, and polyethylene wax is more preferred, from the viewpoint of improving wear resistance.
The melting point of the polyolefin wax is preferably 90 to 160°C, more preferably 100 to 140°C.
These small particle size waxes (C) may be used alone or in combination of two or more.

The small particle size wax (C) may be used in the form of an emulsion dispersed in water.
Furthermore, a commercially available product may be used as the small particle size wax (C). Commercial products include, for example, BASF Japan Co., Ltd.'s product names "Jonkryl Wax 26" and "Jonkryl Wax 28";BYK's product names "AQUACER507", "AQUACER515", "AQUACER526", "AQUACER531", "AQUACER537", "AQUACER539", "AQUACER552", "AQUACER840", "AQUACER1547", "AQUATIX8421"; Product names manufactured by Toho Chemical Industry Co., Ltd. "Hitech E-6314", "Hitech E-1000", "Hitec E- 6500'', ``Hitech E-9015'', ``Hitech E-6400'', ``Hitech E-8237'', ``Hitech E-5403P'', ``Hitech E-4A'', ``Hitech P-9018'', ``Hitech P-5300'' ”, “Hitec P-5800”, and “Hitec P-5060P”.

<Silicone additive (D)>
The silicone additive (D) is used to improve the scratch resistance of the first printed layer.
The silicone additive (D) is a compound having a siloxane bond.
Examples of the silicone additive (D) include polyorganosiloxanes such as polydimethylsiloxane. The polyorganosiloxane may or may not be partially modified with an organic group, but organic modification is preferable because the solubility and dispersibility in the aqueous medium (E) increases. Moreover, although the polyorganosiloxane may be reactive or non-reactive, it is preferable that the polyorganosiloxane be reactive when used in combination with a curing agent (F) described below. Further, the polyorganosiloxane may be in the form of an oil, an emulsion, or a dispersion. The silicone additive (D) may be one copolymerized with an acrylic resin skeleton. In that case, the compatibility with the acrylic resin as the binder resin increases and the transparency improves.
In this specification, polyorganosiloxanes partially modified with organic groups are also referred to as "modified polyorganosiloxanes" or "modified silicones."

Examples of modified polyorganosiloxanes include polyether-modified polyorganosiloxanes, amino-modified polyorganosiloxanes, epoxy-modified polyorganosiloxanes, alkyl-modified polyorganosiloxanes, polyester-modified polyorganosiloxanes, polyether-ester-modified polyorganosiloxanes, and phenyl-modified polyorganosiloxanes. Examples include organosiloxane. Among these, polyether-modified polyorganosiloxane is preferred from the viewpoint of increasing compatibility with components other than the silicone additive (D). Moreover, from the viewpoint of increasing dispersibility in the aqueous medium (E) and reactivity with the hardening agent (F) described below, amino-modified polyorganosiloxane and epoxy-modified polyorganosiloxane are preferable.

As the silicone additive (D), polydimethylsiloxane is preferred, and polyether-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, and epoxy-modified polydimethylsiloxane are more preferred.
These silicone additives (D) may be used alone or in combination of two or more.

As the silicone additive (D), commercially available products may be used. Commercially available products include, for example, BYK product names "BYK302", "BYK-307", "BYK313", "BYK322", "BYK323", "BYK325N", "BYK326", "BYK327", "BYK330", "BYK331", "BYK-333", "BYK342", "BYK-345", "BYK-346", "BYK347", "BYK-348", "BYK349", "BYK-375", "BYK377", "BYK378", "BYK3450", "BYK3451", "BYK3455", "BYK3456", "BYK3760", "BYK3550", "BYK SILCLEAN 3700", "BYK SILCLEAN 3701", "BYK SILCLEAN 3" 720''; Shin-Etsu Chemical Co., Ltd. Company-made product names "KF-351A", "KF-352A", "KF-353", "KF-354L", "KF-355A", "KF-615A", "KF-945", "KF-" 640'', ``KF-642'', ``KF-643'', ``KF-6020'', ``X-22-4515'', ``KF-868'', ``KF-865'', ``KF-864'', ``KF- 859", "KF-393", "KF-860", "KF-880", "KF-8004", "KF-8002", "KF-8005", "KF-867", "KF-869" , "KF-861", "X-22-343", "KF-101", "KF-1001", "X-22-2000", "X-22-3820W", "X-22-3939A" , "KP-124", "KP-109", "KP-110", "KP-121", "KP-118", "KP-341", "KP-112", "KP-125", " KP-101'', ``KP-106'', ``KP-126'', ``KP-360A'', ``KP-361'', ``KP-390'', ``KP-391'', ``KP-392'', ``PAM -E", "KF-8010", "X-22-161A", "X-22-161B", "KF-8012", "KF-8008", "POLON-MF-14", "POLON-MF -14E", "POLON-MF-51", "POLON-MF-14EC", "POLON-MF-63", "KM-9771"; product name "DOWSIL 501W Additive" manufactured by Dow Toray Industries, Inc. DOWSIL FZ-2104 Fluid", "DOWSIL FZ-2110", "DOWSIL FZ-2123", "DOWSIL FZ-2164", "DOWSIL FZ-2191", "DOWSIL FZ-5609 Fluid ”, “DOWSIL L-7001”, "DOWSIL L-7002", "DOWSIL L-7604", "DOWSIL OFX-0309 Fluid", "DOWSIL OFX-5221 Fluid", "DOWSIL SF-8410 Fluid", "DOWSIL OFX-0193 Fluid" d”, “DOWSIL SH- 3746 Fluid”, “DOWSIL SH-3771 Fluid”, “DOWSIL SH-8400 Fluid”, “DOWSIL SH-8700 Fluid”, “DOWSIL Y-7006”, “DOWSIL FZ-2203”, “DOWSIL FZ-2215”, “ DOWSIL FZ-2222”, “DOWSIL BY16-205”, “DOWSIL BY16-213”, “DOWSIL BY16-849 Fluid”, “DOWSIL BY16-853U”, “DOWSIL BY16-871”, “DOWSIL BY16-872”, “ DOWSIL BY16-879B", "DOWSIL BY16-892", "DOWSIL FZ-3705", "DOWSIL FZ-3710 Fluid", "DOWSIL FZ-3785", "DOWSIL SF-8417 Fluid"; E Product name manufactured by VONIK Tegoglide 482''.

<Aqueous medium (E)>
Examples of the aqueous medium (E) include water; a mixed solvent of water and an organic solvent.
The organic solvent in the mixed solvent is not particularly limited as long as it is soluble in water; for example, alcohol solvents such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketone solvents such as acetone; propylene glycol monomethyl Examples include glycol ether solvents such as ether. These organic solvents may be used alone or in combination of two or more.

The content of water relative to the total mass of the aqueous medium is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

<Optional ingredients>
Examples of optional components include thickeners, curing agents (F), antisettling agents, ultraviolet absorbers, antioxidants, leveling agents, viscoelastic modifiers, antifoaming agents, lubricants, dispersants, and stabilizers. .
These optional components may be used alone or in combination of two or more.
In addition, in consideration of visibility, it is preferable that the aqueous varnish composition does not substantially contain a coloring agent such as a pigment.
Here, "substantially not containing" means that no colorant is actively blended, except for those that are unintentionally included.

Thickeners are used to adjust the viscosity of aqueous varnish compositions.
Examples of the thickener include urethane thickeners, polyacrylic thickeners, polyamide thickeners, cellulose thickeners, and clay minerals such as bentonite. Among these, urethane thickeners are more preferred.
The urethane thickener is a so-called associative thickener, and exhibits an effective thickening effect by association of urethane bonds in the aqueous medium (E). Examples of the urethane thickener (urethane association type thickener) include compounds that have a urethane bond and a polyether chain in the molecule and a hydrophobic group at the end. Commercially available urethane thickeners include the product names "SN Thickener 612", "SN Thickener 621N", "SN Thickener 625N", "SN Thickener 627N", and "SN Thickener 660T" manufactured by San Nopco Co., Ltd. .
These thickeners may be used alone or in combination of two or more.

(Curing agent (F))
The curing agent (F) is used to improve the water resistance of the first printed layer.
If the water-based varnish composition further contains the hardening agent (F), workability will be improved compared to the case where the hardening agent (F) is externally added to the water-based varnish composition at the printing site.
In this specification, a water-based varnish composition that does not contain a hardening agent (F) is also referred to as a "first water-based varnish composition", and a water-based varnish composition that contains a hardening agent (F) is also referred to as a "second water-based varnish composition". Also called "composition".

As the curing agent (F), known ones can be used, such as isocyanate curing agents, block isocyanate curing agents, carbodiimide curing agents, oxazoline curing agents, epoxy curing agents, aziridine curing agents, etc. Can be mentioned. Among these, isocyanate-based hardeners, carbodiimide-based hardeners, and oxazoline-based hardeners are preferred, and carbodiimide-based hardeners and oxazoline-based hardeners are more preferred, from the viewpoint of further improving the scratch resistance of the first printed layer.
These curing agents (F) may be used alone or in combination of two or more.

Specific examples of the isocyanate curing agent include the polyvalent isocyanate compounds exemplified above in the description of the water-based acrylic urethane resin.
The isocyanate curing agents may be used alone or in combination of two or more.

Specific examples of blocked isocyanate-based curing agents include blocks of isocyanate-based curing agents (e.g., alcohol-based compounds, phenol-based compounds, oxime-based compounds, lactam-based compounds, pyrazole-based compounds, active methylene compounds, etc.). can be mentioned.
These blocked isocyanate curing agents may be used alone or in combination of two or more.

A carbodiimide curing agent is a compound containing two or more carbodiimide groups in one molecule. Specific examples of carbodiimide curing agents include poly(4,4'-diphenylmethanecarbodiimide), poly(dicyclohexylmethanecarbodiimide), and poly(diisopropylcarbodiimide). Examples of commercially available carbodiimide curing agents include the "Carbodilite" series manufactured by Nisshinbo Chemical Co., Ltd.
These carbodiimide curing agents may be used alone or in combination of two or more.

An oxazoline curing agent is a compound containing two or more oxazoline groups in one molecule. Specific examples of oxazoline curing agents include 2,2'-bis-(2-oxazoline), 2,2'-methylene-bis-(2-oxazoline), and 2,2'-(1,4-phenylene). - Polyvalent oxazolines such as bis(2-oxazoline), oxazoline groups such as 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc. Examples include polymers or copolymers containing monomer units. The oxazoline group-containing monomers may be used alone or in combination of two or more. Alternatively, it may be a copolymer of an oxazoline group-containing monomer and another monomer copolymerizable with this monomer. Examples of commercially available oxazoline curing agents include the "Epocross" series manufactured by Nippon Shokubai Co., Ltd.
These oxazoline curing agents may be used alone or in combination of two or more.

An epoxy curing agent is a compound containing two or more epoxy groups in one molecule. Specific examples of epoxy curing agents include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, triglycidylaminophenol, biphenyl diglycidyl ether, triglycidyl isocyanurate, polyglycidyl (meth)acrylate, and glycidyl (meth)acrylate. Examples include copolymers of this and copolymerizable vinyl monomers. Examples of commercially available epoxy curing agents include the "jER" series manufactured by Mitsubishi Chemical Corporation.
These epoxy curing agents may be used alone or in combination of two or more.

The aziridine curing agent is a compound containing two or more aziridine groups in one molecule. Specific examples of the aziridine curing agent include 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] and 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane. Examples of commercially available aziridine curing agents include the "Chemitite" series manufactured by Nippon Shokubai Co., Ltd.
These aziridine curing agents may be used alone or in combination of two or more.

<Content of each component>
The content of the aqueous binder resin (A) is preferably 80 to 99% by mass, more preferably 83 to 98% by mass, and even more preferably 85 to 97% by mass, based on the total mass of nonvolatile components of the aqueous varnish composition. If the content of the aqueous binder resin (A) is at least the above lower limit, the scratch resistance of the first printing layer is further improved, and in addition, the adhesion to the substrate is improved; The blocking resistance of one printed layer can be easily maintained within an acceptable range.
When the aqueous varnish composition contains an aqueous acrylic resin (a1), the content of the aqueous acrylic resin (a1) is preferably 40 to 99% by mass, and 50 to 99% by mass based on the total mass of nonvolatile components of the aqueous varnish composition. It is more preferably 99% by weight, even more preferably 60-98% by weight, even more preferably 80-98% by weight, particularly preferably 83-97% by weight, and most preferably 85-97% by weight.

The content of the large particle size wax (B) is 5% by mass or less based on the total mass of nonvolatile components of the aqueous varnish composition, preferably 0.2 to 5% by mass, more preferably 0.5 to 4%. Preferably, 1 to 3% by mass is more preferable. If the content of the large particle size wax (B) is more than the above lower limit value, the scratch resistance of the first printed layer will be further improved, and if it is less than the above upper limit value, the transparency and shrinkage of the first printed layer will be improved. Later whitening resistance is improved.

The total content of the large particle wax (B) and the small particle wax (C) (hereinafter also referred to as "B+C") is 0.5 to 8 It is preferably 1% by mass, more preferably 1% to 8% by mass, and even more preferably 2% to 8% by mass. If the total content of the large particle size wax (B) and the small particle size wax (C) is equal to or greater than the above lower limit value, the abrasion resistance will be improved while maintaining transparency, and if it is below the above upper limit value, the wear resistance will be improved. Transparency and resistance to whitening after shrinkage are further improved while maintaining abrasion resistance.

The mass ratio of large particle wax (B) to the mass of small particle wax (C), that is, the mass ratio expressed by large particle wax (B)/small particle wax (C) (hereinafter referred to as "B/ The C ratio (also referred to as "C ratio") is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.3 to 2.5. If the B/C ratio is greater than or equal to the lower limit, the abrasion resistance will be greater than the allowable value, and if it is less than the upper limit, transparency and resistance to whitening after shrinkage can be maintained well within the allowable range.

The content of the silicone additive (D) is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, and 0.2 to 4% by mass based on the total mass of nonvolatile components of the aqueous varnish composition. 3% by mass is more preferred. If the content of the silicone additive (D) is at least the above lower limit value, the scratch resistance of the first printed layer will be further improved, and if it is below the above upper limit value, the whitening resistance after shrinkage will be within an acceptable range. can be maintained.

The content of the aqueous medium (E) is preferably 45 to 80% by weight, more preferably 50 to 75% by weight, even more preferably 60 to 70% by weight, based on the total weight of the aqueous varnish composition. If the content of the aqueous medium (E) is at least the above lower limit, the fluidity of the aqueous varnish composition will be good, and if it is below the above upper limit, the drying properties of the coating film of the aqueous varnish composition will be good.
The content of the alcoholic solvent is preferably 0 to 5% by weight, more preferably 0 to 4% by weight, and even more preferably 0 to 3% by weight based on the total weight of the aqueous varnish composition. When the content of the alcohol solvent exceeds 5% by mass, drying is too rapid during flexographic printing, which tends to cause printing defects such as plate run.

The content of the optional component is not particularly limited as long as it does not impair the effects of the present invention, but for example, it is preferably 0 to 15% by mass, and 0 to 12% by mass based on the total mass of nonvolatile components of the aqueous varnish composition. % is more preferable, and 0 to 10% by mass is even more preferable.
When the aqueous varnish composition contains a thickener as an optional component, the content of the thickener is preferably from 0.01 to 5% by mass, and from 0.05 to 5% by mass based on the total mass of nonvolatile components of the aqueous varnish composition. 3% by mass is more preferred. If the content of the thickener is at least the lower limit above, the effect of the thickener will be fully expressed and the viscosity of the aqueous varnish composition can be easily adjusted to a desired value, and if the content is below the upper limit above, the viscosity of the aqueous varnish composition will be adjusted to a desired value. Good physical properties of the composition can be maintained.
When the aqueous varnish composition contains a curing agent (F) as an optional component, the content of the curing agent (F) is preferably 0.5 to 15% by mass based on the total mass of nonvolatile components of the aqueous varnish composition, More preferably 1 to 10% by mass. If the content of the curing agent (F) is more than the above lower limit value, the effect of the curing agent (F) will be fully expressed and a robust first printing layer will be easily obtained, and if it is less than the above upper limit value, the flexo printing layer will be easily obtained. Printing defects such as plate entanglement can be suppressed during printing.

<Manufacturing method>
The aqueous varnish composition of the present embodiment includes, for example, an aqueous binder resin (A), a large particle size wax (B), a small particle size wax (C), a silicone additive (D), and an aqueous medium (E) as necessary. It can be obtained by mixing one or more optional components depending on the desired content of each component.
The method of mixing each component is not particularly limited, and each component can be mixed by various methods.

<Application>
The aqueous varnish composition of this embodiment is suitable as a varnish for printing on the surface of a base material such as a plastic film by gravure printing or flexographic printing. It is particularly suitable as a varnish for printing on the surface of a base material by flexographic printing. That is, the aqueous varnish composition of this embodiment is suitable for flexographic printing.

<Effect>
As mentioned above, normally, as the particle size of the wax increases and as the wax content increases, the scratch resistance of the printed layer tends to improve, but the transparency tends to decrease.
However, in the case of the aqueous varnish composition of the present embodiment, the wax component contains both the large particle size wax (B) and the small particle size wax (C), and also contains the large particle size wax (B). The amount is 5% by weight or less based on the total weight of nonvolatile components of the aqueous varnish composition. Therefore, without using a wax with too large a particle size or excessively increasing the content of the large particle wax (B), the aqueous wax of this embodiment can be used in combination with the small particle wax (C). The first printed layer formed using the varnish composition can exhibit sufficient scratch resistance. Further, since it is not necessary to use a wax having an excessively large particle diameter or to excessively increase the content of the large particle diameter wax (B), the transparency of the first printing layer can also be maintained satisfactorily. Since the first printed layer, which has excellent transparency, does not easily whiten even if it is shrunk, the first printed layer also has excellent resistance to whitening after shrinking.
In addition, the aqueous varnish composition of the present embodiment contains, in addition to the above-mentioned large particle size wax (B) and small particle size wax (C), the above-mentioned aqueous binder resin (A) and silicone additive (D). and an aqueous medium (E), it is possible to form a first printed layer that is excellent in transparency, whitening resistance after shrinkage, and scratch resistance.
In particular, if the aqueous varnish composition further contains the above-mentioned curing agent (F), it is possible to form a first printed layer that also has excellent water resistance.

[kit]
A kit according to one embodiment of the present invention contains the above-described aqueous varnish composition of the present invention and a curing agent (F), each independently.
Here, "independently" means that the aqueous varnish composition and the curing agent (F) are present in a state where they are not in contact with each other. For example, the kit contains the aqueous varnish composition. 1 container and a second container containing a curing agent (F).

The aqueous varnish composition constituting the kit may or may not contain a curing agent (F) as an optional component, but considering the storage stability of the aqueous varnish composition, the aqueous varnish composition constituting the kit Preferably, the varnish composition does not contain a curing agent (F). That is, the first aqueous varnish composition is preferable as the aqueous varnish composition constituting the kit. Further, the kit preferably includes a first container containing the first aqueous varnish composition and a second container containing the hardening agent (F).
Examples of the curing agent (F) constituting the kit include the curing agent (F) exemplified above as an example of an optional component in the aqueous varnish composition of the present invention.

The second container may contain components other than the curing agent (F) (other components).
Examples of other components include solvents, stabilizers, and the like.
Examples of the solvent include the aqueous medium (E) exemplified above in the description of the aqueous varnish composition.

The kit is used by mixing the aqueous varnish composition and hardening agent (F) at the time of use.
When mixing the water-based varnish composition and the hardening agent (F), the ratio of the hardening agent (F) to 100 parts by mass of the nonvolatile content of the water-based varnish composition is 0.5 to 15 parts by mass. , it is preferable to mix both, more preferably 1 to 10 parts by weight, still more preferably 1 to 9.5 parts by weight. If the ratio of the curing agent (F) is at least the above-mentioned lower limit, the curing reaction will proceed sufficiently, and if it is below the above-mentioned upper limit, the water resistance of the first printed layer will be further improved.

<Effect>
The kit of the present embodiment described above is a so-called two-component varnish that independently contains the aqueous varnish composition of the present invention and the curing agent (F), and if the kit of the present embodiment is used, The first printing layer has excellent transparency, whitening resistance after shrinkage, scratch resistance, and water resistance.
Furthermore, by using the aqueous varnish composition of the present invention as a two-component varnish, the first printing on a base material such as a plastic film, which will be described later, is more effective than a one-component varnish that does not contain a curing agent (F). Improves layer adhesion. In addition, the strength of the first printed layer itself is increased.

[Article with printed layer]
FIG. 1 shows an example of an article with a printed layer according to an embodiment of the present invention. Note that the dimensional ratio in FIG. 1 is different from the actual one for convenience of explanation.
The article 10 with a printed layer of this example includes a plastic film 11 as a base material, a first printed layer 12 provided on a first surface 11a of the plastic film 11, and a first printed layer 12 provided on a second surface 11b of the plastic film 11. and a second printed layer 13 provided thereon.
Note that in this specification, the first surface 11a of the plastic film 11 is also referred to as the "front surface", and the second surface 11b of the plastic film 11 is also referred to as the "back surface".

<Plastic film>
The type of plastic film 11 can be appropriately selected depending on the type of the printed layer-equipped article 10, and is not particularly limited, but for example, the printed layer-equipped article 10 can be used as a heat-shrinkable label (shrink label). In this case, the plastic film 11 is preferably a heat-shrinkable film (shrink film). When the printed layer-equipped article 10 is used as a stretch label, the plastic film 11 is preferably a stretch film. Among these, the plastic film 11 is preferably a heat-shrinkable film.

Examples of the plastic film 11 include polyester films such as polyethylene terephthalate (PET), amorphous polyethylene terephthalate (A-PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polylactic acid; low-density polyethylene ( Polyolefin films such as LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polypropylene (PP); cellulose films such as cellophane; polystyrene (PS) films; ethylene-vinyl acetate copolymer resin films ; ethylene-vinyl alcohol copolymer resin film; polyamide (Ny) film; polycarbonate film; polyimide film; polyvinyl chloride film. These films can be appropriately selected depending on the purpose. For example, when the article 10 with a printed layer is used as a heat-shrinkable label (shrink label), the plastic film 11 may be a uniaxially shrinkable polystyrene film, a uniaxially shrinkable PET film, a uniaxially shrinkable polyolefin film, a uniaxially shrinkable polyolefin film, or a uniaxially shrinkable polyolefin film. Vinyl chloride film is preferred.
As the plastic film 11, both stretched and unstretched plastic films can be used, such as biaxially stretched PP films and unstretched PP films. The surface of the plastic film 11 may be subjected to surface treatments such as corona discharge treatment, plasma treatment, flame treatment, and solvent treatment.

The plastic film 11 may have a single layer structure or a laminated structure. That is, the plastic film 11 may be a single layer film or a laminated film. When the plastic film 11 is a laminated film, it may have a structure in which two or more films of the same type are laminated, or a structure in which two or more films of different types are laminated. Examples of preferred combinations of films include a combination in which a polyester film is used as the front side of the plastic film 11 and a polystyrene film or a polyolefin film is used as the back side of the plastic film 11, a combination in which a cyclic polyolefin film is used as the front side of the plastic film 11, and a polyethylene film is used as the front side of the plastic film 11. Alternatively, a combination in which a polypropylene film is used as the back side of the plastic film 11 may be mentioned.

The thickness of the plastic film 11 is preferably 12 to 100 μm, more preferably 12 to 60 μm, and even more preferably 12 to 50 μm.

<First printing layer>
The first printed layer 12 is provided on the first surface 11a of the plastic film 11.
The first printed layer 12 is a printed layer formed using the aqueous varnish composition or kit of the present invention described above, and serves as a protective layer.
The thickness of the first printed layer 12 is preferably 0.3 to 3.0 μm, more preferably 0.3 to 2.0 μm, and even more preferably 0.3 to 1.5 μm.

<Second printing layer>
The second printed layer 13 is provided on the second surface 11b of the plastic film 11.
The second printed layer 13 may be formed using the above-described aqueous varnish composition or kit of the present invention, or may be formed using another varnish composition, but the printed layer provided article 10 It is preferable that the ink composition is used to impart design properties, functionality, etc. to the ink composition. That is, the second printing layer 13 is preferably a printing layer (picture layer) formed using an ink composition.
The second printed layer 13 may have a single layer structure or a laminated structure.
The total thickness of the second printed layer 13 is preferably 0.3 to 15 μm, more preferably 0.3 to 10 μm, and even more preferably 0.3 to 8 μm.

The ink composition is preferably an aqueous ink composition.
The aqueous ink composition is not particularly limited and any known one can be used, but examples include compositions containing an aqueous binder resin, an aqueous medium, a colorant, and other components as necessary. .
Examples of the aqueous binder resin include the aqueous binder resin (A) exemplified above in the description of the aqueous varnish composition of the present invention.
Examples of the aqueous medium include the aqueous medium (E) exemplified above in the description of the aqueous varnish composition of the present invention.
Examples of colorants include azo pigments (monoazo, condensed azo, etc.), threne pigments (anthraquinone, perinone, perylene, thioindigo, etc.), phthalocyanine pigments (phthalocyanine blue, phthalocyanine green, etc.), and quinacridone pigments. , dioxazine pigments, isoindolinone pigments, pyrrolopyrrole pigments, aniline black, organic pigments such as organic fluorescent pigments; natural products (clay, etc.), ferrocyanides (prussian blue, etc.), sulfides (zinc sulfide, etc.), Sulfates, oxides (chromium oxide, zinc white, titanium oxide, iron oxide, etc.), hydroxides (aluminum hydroxide, etc.), silicates (ulmarine, etc.), carbonates, carbon (carbon black, graphite, etc.), Examples include metal powders (aluminum powder, bronze powder, zinc powder, etc.) and inorganic pigments such as fired pigments.
Examples of other components include waxes, dispersants, antifoaming agents, lubricants, and lubricants.

<Manufacturing method>
The method for manufacturing the printed layer-equipped article 10 according to the present embodiment includes a step (1) of forming the first printed layer 12 on the first surface 11a of the plastic film 11 using the aqueous varnish composition or kit of the present invention. ), and a step (2) of forming a second printed layer 13 on the second surface 11b of the plastic film 11.
The order of step (1) and step (2) is not particularly limited, and step (2) may be performed after step (1), or step (1) may be performed after step (2). .

In step (1), for example, the aqueous varnish composition of the present invention is applied to the first surface 11a of the plastic film 11 and dried to form the first printed layer 12.
When forming the first printed layer 12 using the kit of the present invention, a mixture is prepared by mixing the aqueous varnish composition included in the kit and a curing agent (F), and the resulting mixture is applied to the plastic film 11. The first printed layer 12 may be formed by coating the first surface 11a of the first surface 11a and drying the first surface 11a. The mixing ratio when mixing the water-based varnish composition and the hardening agent (F) is as described above.

The method for applying the aqueous varnish composition or mixture is not particularly limited, and includes, for example, gravure printing, flexographic printing, brush coating, gravure coater method, die coater method, bar coater method, spray coating method, flow coating method, and dip coating method. , a spin coating method, a curtain coating method, and other known coating methods can be used. Among these, flexo printing is preferred due to its high quality and productivity.

The drying method is not particularly limited as long as it can remove the aqueous medium (E) contained in the aqueous varnish composition or mixture coated on the first surface 11a of the plastic film 11, but for example, drying under reduced pressure, drying under pressure, heating, etc. Examples include drying and air drying.
The heating temperature is preferably 30 to 150°C, more preferably 40 to 100°C.

In step (2), for example, a water-based ink composition is applied to the second surface 11b of the plastic film 11 and dried to form the second printed layer 13.
The method for applying the water-based ink composition includes the same method as the method for applying the water-based varnish composition or mixture.
The drying method is not particularly limited as long as the aqueous medium contained in the aqueous ink composition coated on the second surface 11b of the plastic film 11 can be removed, and examples include methods similar to those for drying the aqueous varnish composition. .

<Application>
The article 10 with a printed layer can be used as a plastic label attached to packaging containers for beverages, foods such as side dishes and lunch boxes, and daily necessities such as cosmetics. In particular, when the plastic film 11 constituting the printed layer-attached article 10 is a heat-shrinkable film, it is suitable as a shrink label.

<Effect>
In the printed layer-equipped article of the present embodiment described above, the first printed layer formed using the above-described aqueous varnish composition or kit of the present invention is provided on the first surface of the plastic film. Since the first printed layer has excellent scratch resistance, the article with the printed layer is less likely to be damaged. Moreover, since the first printed layer has excellent transparency, it is easy to visually recognize the second printed layer provided on the second surface of the plastic film. In particular, when the plastic film is a heat-shrinkable film and the article with a printed layer is used as a shrink label, the first printed layer has excellent resistance to whitening after shrinkage, so even if the article with the printed layer shrinks, The second printed layer is easily visible.

<Other embodiments>
The article with a printed layer is not limited to the embodiments described above.
For example, an article with a printed layer may not include a second printed layer.
Further, in the case of the article 10 with a printed layer shown in FIG. 1, the first printed layer 12 is provided on the entire first surface 11a of the plastic film 11; It may be provided in a part of the first surface 11a. In this case, it is preferable that another printed layer is provided in the region of the first surface 11a of the plastic film 11 where the first printed layer 12 is not provided. The other printing layer is preferably formed using a composition containing a matting agent such as an extender pigment.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the following, "NV" refers to non-volatile content.

[Raw materials used]
The following compounds were used as the aqueous binder resin (A).
・A-1: Water-based acrylic emulsion resin (manufactured by BASF Japan Co., Ltd., product name "Joncryl PDX-7430", weight average molecular weight > 200000, glass transition temperature 30°C, minimum film forming temperature 44°C, acid value 20mgKOH/g , nonvolatile content 38% by mass).
・A-2: Water-based acrylic emulsion resin (manufactured by BASF Japan Co., Ltd., trade name "Joncryl PDX-7356", weight average molecular weight 100,000 to 200,000, glass transition temperature 40 ° C., acid value 78 mgKOH/g, non-volatile content 45.5 mass%).
- A-3: Water-based acrylic urethane emulsion resin (manufactured by Taisei Fine Chemical Co., Ltd., trade name "WEM-200U", glass transition temperature 27°C, acid value 16 mgKOH/g, nonvolatile content 38% by mass).
・A-4: Water-based acrylic emulsion resin (manufactured by BASF Japan Co., Ltd., product name "Joncryl PDX-7696", weight average molecular weight 100,000 to 200,000, glass transition temperature 86°C, minimum film forming temperature 26°C, acid value 122mgKOH/ g, non-volatile content 40% by mass).

The compound shown below was used as the large particle size wax (B).
- B-1: Polyethylene wax (manufactured by Mitsui Chemicals, Inc., trade name "Chemipearl W400", volume average particle diameter 4 μm, non-volatile content 40% by mass, hardness 3 by penetration method, softening point 110° C. by ring and ball method).
- B-2: Polyethylene wax (manufactured by Mitsui Chemicals, Inc., trade name "Chemipearl W500", volume average particle diameter 4 μm, non-volatile content 40% by mass, hardness 10 by penetration method, softening point 113° C. by ring and ball method).
The volume average particle diameter of the large particle size wax (B) is the particle diameter at a cumulative frequency of 50% on a volume basis, which is calculated from the particle size distribution obtained by measuring the volume-based particle size distribution by the Coulter counter method. (median diameter: D50).

The following compound was used as the small particle size wax (C).
- C-1: Polyethylene wax (manufactured by BASF Japan Co., Ltd., trade name "Jonkryl Wax 26", volume average particle diameter 0.05 μm, non-volatile content 25% by mass, melting point 130° C.).
- C-2: Polyethylene wax (manufactured by BYK, trade name "AQUACER537", volume average particle diameter 0.061 μm, non-volatile content 30% by mass, melting point 110°C).
The volume average particle diameter of the small particle size wax (C) is determined by measuring the volume-based particle size distribution using a dynamic light scattering method, and calculating the volume-based cumulative frequency of 50% from the obtained particle size distribution. Particle diameter (median diameter: D50).

The following compounds were used as the silicone additive (D).
- D-1: Silicone modified copolymer (manufactured by EVONIK, trade name "Tegoglide 482", non-volatile content 65% by mass).
- D-2: Amino-modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KF-868", nonvolatile content 100% by mass).
- D-3: Hydroxyl group-containing silicone-modified acrylic (manufactured by BYK, trade name "BYK SILCLEAN 3700", nonvolatile content 25% by mass).

The following compounds were used as the thickener, curing agent (F), and aqueous medium (E).
- Thickener: Urethane association type thickener (manufactured by San Nopco Co., Ltd., trade name "SN Thickener 612", non-volatile content 40% by mass).
- F-1: Carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd., trade name "Carbodilite E-02", non-volatile content 40% by mass).
-F-2: Oxazoline curing agent (manufactured by Nippon Shokubai Co., Ltd., trade name "Epocross WS-500", non-volatile content 39% by mass).
・E-1: Water.

[Evaluation method]
<Transparency evaluation>
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd., product name "HZ-2 type") and a D65 light source, the haze value of the surface of the first printed layer side of the printed matter before shrinkage was measured, and the following The transparency of the first printed layer was evaluated based on the following evaluation criteria. If it is 〇 or △, it is practical.
○: Haze value is less than 10%.
Δ: Haze value is 10% or more and less than 15%.
×: Haze value is 15% or more.

<Evaluation of whitening resistance after shrinkage>
A 20 cm printed material was immersed in hot water at 90° C. for 30 seconds to shrink it to 15 cm. For the printed matter after shrinkage, use a haze meter (manufactured by Suga Test Instruments Co., Ltd., product name "HZ-2 type") and a D65 light source to measure the haze value of the surface of the first printed layer side of the printed matter. The difference in haze value was determined by subtracting the haze value of the printed matter before shrinkage from the haze value of the printed matter after shrinkage, and the whitening resistance of the first printed layer after shrinkage was evaluated using the following evaluation criteria. If ◎, 〇 or △, it is practical.
◎: Difference in haze value is less than 50%.
○: Haze value is 50% or more and less than 100%.
Δ: Difference in haze value is 100% or more and less than 200%.
×: Difference in haze value is 200% or more.

<Evaluation of scratch resistance>
Two test pieces of the same size were cut out from the printed matter. Each test piece was placed with the first printed layer facing each other, and one of the test pieces was The other test piece was reciprocated 1000 times under a load of 500 g while being fixed. After that, the number of scratches that occurred on the first printed layer of each test piece and the degree of peeling of the first printed layer were visually confirmed, and the scratch resistance of the first printed layer was evaluated using the following evaluation criteria. evaluated. If ○, it is practical.
○: The number of scratches is less than 20.
×: The number of scratches is 20 or more, or the first printed layer is peeled off from the plastic film and the plastic film is torn.

<Evaluation of adhesion>
After pasting cellophane tape (manufactured by Nichiban Co., Ltd.) with a width of 18 mm on the surface of the first printing layer side of the printed matter and pressing it with your fingers, quickly peel off this cellophane tape and remove the first print that remained on the plastic film. The state of the layer was visually confirmed, and the adhesion of the first printed layer to the base material was evaluated using the following evaluation criteria. If ◎, 〇 or △, it is practical.
◎: The first printed layer was not peeled off at all.
O: The ratio of the area of the first printed layer peeled off from the plastic film to the adhesive area of the cellophane tape (peeling ratio) is more than 0% and less than 20%.
Δ: The ratio of the area of the first printed layer peeled off from the plastic film (peeling ratio) to the adhesive area of the cellophane tape is 20% or more and less than 70%.
×: The ratio of the area of the first printed layer peeled off from the plastic film to the adhesive area of the cellophane tape (peeling ratio) is less than 70%.

<Evaluation of adhesion after shrinkage>
A 20 cm printed material was immersed in hot water at 90° C. for 30 seconds to shrink it to 15 cm. For the printed matter after shrinkage, a cellophane tape (manufactured by Nichiban Co., Ltd.) with a width of 18 mm was pasted on the surface of the first printing layer side and pressed with a finger, and then this cellophane tape was quickly peeled off to remove the cellophane tape that remained on the plastic film. The state of the first printed layer was visually confirmed, and the adhesion of the first printed layer to the base material was evaluated using the following evaluation criteria. If ◎, 〇 or △, it is practical.
◎: The first printed layer was not peeled off at all.
O: The ratio of the area of the first printed layer peeled off from the plastic film to the adhesive area of the cellophane tape (peeling ratio) is more than 0% and less than 20%.
Δ: The ratio of the area of the first printed layer peeled off from the plastic film (peeling ratio) to the adhesive area of the cellophane tape is 20% or more and less than 70%.
×: The ratio of the area of the first printed layer peeled off from the plastic film to the adhesive area of the cellophane tape (peeling ratio) is less than 70%.

<Evaluation of water resistance>
A water resistance test was conducted by placing tap water in a sealed container, immersing the printed material, and storing it in an environment of 40° C. for 24 hours. Changes in the first printed layer after the water resistance test were visually observed, and the water resistance of the first printed layer was evaluated based on the following evaluation criteria. If it is 〇 or △, it is practical.
○: The first printed layer has not changed.
Δ: The first printed layer is whitened, and the difference in haze value before and after the water resistance test is less than 20 % .
×: The first printed layer is whitened, and the difference in haze value before and after the water resistance test is 20 % or more, or the first printed layer is detached from the film.

<Evaluation of blocking resistance>
The uniaxially shrinkable PET film (manufactured by Toyobo Co., Ltd., trade name "Toyobo Space Clean S7053", thickness 40 μm) and the surface of the first printing layer side of the printed matter overlap, so that the uniaxially shrinkable PET film and the printed matter are overlapped. were placed on top of each other and left in a constant temperature bath at 40° C. for 24 hours under a load of 4 kg/cm ² . Next, the blocking resistance was evaluated based on the peeling resistance when the uniaxially shrinkable PET film and the printed matter were peeled off, and the change in appearance of the first printed layer of the printed matter based on the following evaluation criteria. If ◎, 〇 or △, it is practical.
◎: There is no peeling resistance, and no transfer of the first printed layer to the uniaxially shrinkable PET film is observed.
Good: Very slight peeling resistance is felt, but no transfer of the first printed layer to the uniaxially shrinkable PET film is observed.
Δ: Some peeling resistance is felt, but no transfer of the first printed layer to the uniaxially shrinkable PET film is observed.
×: Considerable peeling resistance was observed, and transfer of the first printed layer to the uniaxially shrinkable PET film was observed.

[Examples 1 to 17, Comparative Examples 1 to 8]
<Preparation of water-based varnish composition>
According to the formulations shown in Tables 1 to 3, aqueous binder resin (A), large particle size wax (B), small particle size wax (C), silicone additive (D), optional ingredients, and aqueous medium (E) to obtain an aqueous varnish composition.
Note that the aqueous varnish compositions obtained in Examples 1 to 14 and 17 are the first aqueous varnish compositions. Among them, the aqueous varnish compositions obtained in Examples 8 to 10 are the first aqueous varnish compositions containing an aqueous acrylic resin (a1) and an aqueous acrylic resin (a2) as the aqueous binder resin (A). In the case of Example 8, the a1/a2 ratio is 7.5. In the case of Example 9, the a1/a2 ratio is 2.4. In the case of Example 10, the a1/a2 ratio is 0.9.
The aqueous varnish compositions obtained in Examples 15 and 16 are the second aqueous varnish compositions.
Moreover, a blank column in the table means that the component is not blended (blended amount: 0 parts by mass).
Tables 1 to 3 show the content of each component in the aqueous varnish composition relative to the total mass of nonvolatile components of the aqueous varnish composition.

For Examples 13 and 14, a curing agent (F) of the type and amount shown in Table 2 was mixed with 100 parts by mass of the obtained aqueous varnish composition (first aqueous varnish composition), A mixture was prepared. In the case of Example 13, the ratio of the curing agent (F) to 100 parts by mass of the nonvolatile content of the aqueous varnish composition (first aqueous varnish composition) was 9.4 parts by mass. In the case of Example 14, the ratio of the curing agent (F) to 100 parts by mass of the nonvolatile content of the aqueous varnish composition (first aqueous varnish composition) was 9.1 parts by mass.

<Preparation of printed matter>
As the plastic film, a uniaxially shrinkable PET film (manufactured by Toyobo Co., Ltd., trade name "Toyobo Space Clean S7053", thickness 40 μm) was used.
Using a flexographic hand proofer equipped with an anilox roll with a cell volume of 6.0 cm ³ /m ² as an applicator, the aqueous varnish composition or mixture was applied to the first side of the plastic film at a coating weight of 1.0 g/m after drying. It was coated so that it became ² . Next, it was dried at 25° C. for 72 hours to form a first printing layer with a thickness of about 0.85 μm on the first surface of the plastic film, thereby obtaining a printed matter.
Using the obtained printed matter, transparency, whitening resistance after shrinkage, scratch resistance, adhesion, adhesion after shrinkage, water resistance, and blocking resistance were evaluated. The results are shown in Tables 1 to 3.

As is clear from the results in Tables 1 and 2, the aqueous varnish compositions or mixtures obtained in each example were able to form a first printing layer with excellent transparency, whitening resistance after shrinkage, and scratch resistance. Ta.
In particular, the first printed layers obtained in Examples 8 to 10 using a combination of aqueous acrylic resin (a1) and aqueous acrylic resin (a2) as the aqueous binder resin (A) also had excellent blocking resistance.
Furthermore, the first printed layers obtained in Examples 13 to 16 in which the curing agent (F) was used also had excellent water resistance.

On the other hand, as is clear from the results in Table 3, the first printed layer formed from the aqueous varnish compositions obtained in Comparative Examples 1 and 6, which did not contain the small particle size wax (C), had poor scratch resistance. It was inferior.
The first printed layer formed from the aqueous varnish compositions obtained in Comparative Examples 2, 7, and 8 that did not contain the large particle size wax (B) had poor scratch resistance.
The first printed layer formed from the aqueous varnish composition obtained in Comparative Example 3 that did not contain the silicone additive (D) had poor scratch resistance.
The first printed layer formed from the aqueous varnish composition obtained in Comparative Example 4 in which the content of the large particle size wax (B) exceeded 5% by mass was inferior in transparency and resistance to whitening after shrinkage. .
The first printing layer was formed from the aqueous varnish composition obtained in Comparative Example 5 in which the content of the large particle size wax (B) exceeded 5% by mass and did not contain the small particle size wax (C). , transparency and resistance to whitening after shrinkage were poor.

10 Article with printed layer 11 Plastic film 11a First surface 11b Second surface 12 First printed layer 13 Second printed layer

Claims (16)

Water-based binder resin (A), large particle size wax (B) with an average particle size of 1 to 8 μm, small particle size wax (C) with an average particle size of 0.005 to 0.3 μm, and silicone additive An aqueous varnish composition containing (D) and an aqueous medium (E),
An aqueous varnish composition in which the content of the large particle size wax (B) is 5% by mass or less based on the total mass of nonvolatile components of the aqueous varnish composition. The aqueous varnish composition according to claim 1, wherein the mass ratio expressed by the large particle wax (B)/the small particle wax (C) is 0.1 to 10. The total content of the large particle wax (B) and the small particle wax (C) is 0.5 to 8% by mass based on the total nonvolatile content of the aqueous varnish composition. 3. The aqueous varnish composition according to 1 or 2. The aqueous varnish composition according to claim 1 or 2, wherein the content of the silicone additive (D) is 0.1 to 5% by mass based on the total mass of nonvolatile components of the aqueous varnish composition. The aqueous varnish composition according to claim 1 or 2, wherein the silicone additive (D) contains polydimethylsiloxane. The aqueous varnish composition according to claim 1 or 2, wherein the aqueous binder resin (A) contains at least one of an acrylic resin emulsion and an acrylic urethane resin emulsion. The aqueous varnish composition according to claim 1 or 2, wherein at least one of the large particle size wax (B) and the small particle size wax (C) contains a polyolefin wax. The aqueous varnish composition according to claim 1 or 2, which is used for flexographic printing. The aqueous varnish composition according to claim 1 or 2, further comprising a hardening agent (F). A kit comprising independently the aqueous varnish composition according to claim 1 and a hardening agent (F). An article with a printed layer, wherein a first printed layer formed using the aqueous varnish composition according to claim 1 or 2 or the kit according to claim 10 is provided on a first side of a plastic film. The article with a printed layer according to claim 11, wherein a second printed layer is provided on the second side of the plastic film. The article with a printed layer according to claim 11, wherein the plastic film is a heat-shrinkable film. A method for producing an article with a printed layer, the method comprising forming a first printed layer on a first surface of a plastic film using the aqueous varnish composition according to claim 1 or 2 or the kit according to claim 10. . The method for producing an article with a printed layer according to claim 14, further comprising the step of forming a second printed layer on the second surface of the plastic film. The method for producing an article with a printed layer according to claim 14, wherein the plastic film is a heat-shrinkable film.

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