JP7194310B1 - Aqueous printing ink composition for surface printing film - Google Patents

Abstract

[Problem] To provide a water-based ink composition for surface printing on a film, the water-based printing ink composition improving the blocking resistance of the resulting printed layer and further improving the heat resistance and the water and abrasion resistance. provide. A water-based printing ink composition for a surface printing film containing a water-based binder resin and a water-based medium, further comprising acyl taurinate and/or acyl amino acid salt having an acyl group having 10 to 20 carbon atoms. Provided is a water-based printing ink composition for surface printing film containing 0.3 to 10.0% by mass of the ink composition. [Selection drawing] Fig. 1

Description

The present invention relates to an aqueous printing ink composition for surface printing films, for printing on one or both sides of the film.

Various products (food, confectionery, household goods, pet food, etc.) are packaged with packaging materials using various plastic films to enhance product design, economy, content protection, transportability, and the like. Gravure printing and flexographic printing are applied to many packaging materials with the intention of imparting design and message appealing to consumers. These packaging materials are surface-printed on the surface of the base film of the packaging material (the surface that will be the outside when packaged), or a printed layer formed on the surface of the base film of the packaging material, if necessary. Adhesives and anchoring agents are applied as necessary, and further lamination is applied.

Printing inks for surface printing on substrate films are often solvent-based inks, but in recent years water-based printing inks for surface printing films have been studied from the standpoint of environmental concerns. For example, 1) a water-based printing ink composition for surface printing films containing a hydrazine compound and a carbodiimide compound (see Patent Document 1), 2) water-based printing for surface printing films containing a styrene-acrylic resin emulsion having a core-shell structure. An ink composition (see Patent Document 2), 3) a water-based printing ink composition for surface printing films containing a specific anionic surfactant (see Patent Document 3), and the like have been proposed.

JP 2018-076431 A JP 2017-190416 A JP 2020-059822 A

However, conventional water-based printing ink compositions for surface printing films have not taken into consideration the improvement of blocking resistance. In recent years, in particular, there have been double-sided printed films having printed layers on both sides of a base film. Blocking properties are required, and water-based printing ink compositions for surface printing films are also required to have higher blocking resistance.

Accordingly, an object of the present invention is to provide a water-based ink composition for surface-printing films for printing on one side or both sides of a film, which can improve the blocking resistance of the resulting printed layer and further improve the heat resistance. , to provide a water-based printing ink composition for surface printing films.

（式Iにおいて、
R1は、炭素数９～１９のアルキル基、アルケニル基、アルキニル基、芳香族炭化水素基を示し；
R２は、水素原子又は低級アルキル基を示し；
Mはスルホン酸に対するカウンターイオンを示す。）

（式IIにおいて、
R３は、炭素数９～１９のアルキル基、アルケニル基、アルキニル基、芳香族炭化水素基を示し；
R４は、水素原子又は低級アルキル基を示し；
R５は、水素原子又は低級アルキル基を示し、当該低級アルキル基は、ヒドロキシル基、カルボキシル基又はスルフヒドリル基を有していてもよく；
Mはカルボン酸に対するカウンターイオンを示す。） The present inventors have made intensive studies to solve the above problems, and as a result, have found the following water-based printing ink composition for surface printing films.
[1] An aqueous printing ink composition for surface printing film containing an aqueous binder resin and an aqueous medium, further comprising an acyl taurinate (formula I) and/or acyl having an acyl group having 10 to 20 carbon atoms An aqueous printing ink composition for surface printing films, containing 0.3 to 10.0% by mass of an amino acid salt (formula II) in the ink composition.

(In formula I,
R1 represents an alkyl group, alkenyl group, alkynyl group or aromatic hydrocarbon group having 9 to 19 carbon atoms;
R2 represents a hydrogen atom or a lower alkyl group;
M indicates a counter ion for sulfonic acid. )

(In Formula II,
R3 represents an alkyl group having 9 to 19 carbon atoms, an alkenyl group, an alkynyl group, or an aromatic hydrocarbon group;
R4 represents a hydrogen atom or a lower alkyl group;
R5 represents a hydrogen atom or a lower alkyl group, and the lower alkyl group may have a hydroxyl group, a carboxyl group or a sulfhydryl group;
M indicates a counter ion for carboxylic acid. )

[2] The water-based printing ink composition for surface printing film according to [1], which contains 0.5 to 10.0% by mass of the acyl taurinate and/or acyl amino acid salt in the ink composition.
[3] The water-based printing ink composition for surface printing film according to [1] or [2], further comprising a phosphate surfactant.
[4] The water-based binder resin according to any one of [1] to [3], wherein the water-based binder resin is at least one selected from water-based acrylic resin emulsions, water-based urethane-based resin emulsions, and water-based acrylic urethane-based resin emulsions. Aqueous printing ink composition for surface printing film.
[5] The water-based printing ink composition for surface printing films according to any one of [1] to [4], further comprising a cross-linking agent.

The water-based printing ink composition for surface printing films of the present invention can form a printed layer on a substrate film by printing on one side or both sides of the film; the printed layer has high blocking resistance, and It can exhibit excellent adhesion to resin films, heat resistance, and water resistance and abrasion resistance in a well-balanced manner.

FIG. 2 is a diagram showing a surface printing film in a wound state and a layer cross-section of the surface printing film; FIG. 2 is a view showing a cylindrical surface printing film in a wound state and a layer cross-section of the surface printing film;

[1. Water-based printing ink composition for surface printing film]
The aqueous printing ink composition for surface printing film of the present invention (also referred to as "aqueous printing ink composition") comprises 1) an aqueous binder resin, and 2) acyl taurinate and/or acyl amino acid salt having a specific acyl group. 3) an aqueous medium, and 4) may contain other optional components. In particular, when the water-based printing ink composition of the present invention is a colored ink composition, it contains a pigment, but when it is a varnish composition, it may not contain a pigment.

[1-1. Water-based binder resin]
The water-based binder resin contained in the water-based printing ink composition of the present invention contains a water-based resin emulsion, and can also be used in combination with a water-soluble resin, if necessary.

[1-1-1. Aqueous resin emulsion]
The content of the water-based resin emulsion in the water-based printing ink composition is preferably 5% by mass or more, more preferably 10% by mass or more as a solid content, when the water-based printing ink composition contains a pigment. Yes; On the other hand, it is preferably 30% by mass or less, more preferably 25% by mass or less. Further, the content of the aqueous resin emulsion in the aqueous printing ink composition is preferably 10% by mass or more as a solid content when the aqueous printing ink composition (varnish composition) does not contain a pigment. , more preferably 15% by mass or more; on the other hand, it is preferably 35% by mass or less, more preferably 30% by mass or less.

Examples of water-based resin emulsions include a) water-based acrylic resin emulsions, b) water-based urethane-based resin emulsions, and c) water-based acrylic urethane-based resin emulsions. In the aqueous resin emulsion, the average particle size of the resin particles is not particularly limited, but is, for example, in the range of 60 nm to 1000 nm, preferably in the range of 60 nm to 400 nm, but is not particularly limited. The average particle size of resin particles refers to a value measured by a dynamic light scattering method.

[1-1-1-1. Water-based acrylic resin emulsion]
The water-based acrylic resin emulsion refers to a resin liquid in which the water-based acrylic resin is emulsified and stabilized in the form of particles. The water-based acrylic resin emulsion in the water-based printing ink composition for surface printing film has an acid group (usually a carboxyl group), and part or all of the acid group is a basic compound (preferably a volatile basic compound).

The water-based acrylic resin emulsion in the water-based printing ink composition preferably has an acid value of 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more; /g or less, more preferably 100 mgKOH/g or less, and even more preferably 90 mgKOH/g or less. When the acid value is 10 mgKOH/g or more, sufficient dispersibility of the aqueous acrylic resin emulsion in an aqueous medium is likely to be obtained. On the other hand, when the acid value is 180 mgKOH/g or less, the stability of the water-based printing ink composition is likely to be obtained.

The acid value of the water-based acrylic resin emulsion is determined, for example, by determining the theoretical amount of neutralization of KOH with respect to the amount of each ethylenically unsaturated monomer theoretically required to obtain 1 g of the copolymer. It can be calculated by regarding the number of mg of the sum total of the sum amounts as the acid value of the copolymer (also referred to as "theoretical acid value"). Incidentally, with respect to water-based acrylic resin emulsions available on the market, the acid value published by the supplier is not necessarily the theoretical acid value, but may be regarded as the theoretical acid value.

The water-based acrylic resin emulsion in the water-based printing ink composition preferably has a glass transition temperature of −30° C. or higher, more preferably −25° C. or higher; It is preferably 120° C. or less. When the glass transition temperature is −30° C. or higher, sufficient heat resistance and adhesiveness are easily imparted to the printed layer, and when it is 150° C. or lower, flexibility is imparted to the printed layer, and the printed layer bends the base film. etc. will be easier to follow.

The glass transition temperature of the water-based acrylic resin emulsion is preferably the theoretical glass transition temperature determined by the following Wood's formula.
Wood's formula:
₁ /Tg ₌ W1 _/ Tg1 ₊ W2/ _Tg2 +W3/ _Tg3 +...+ _Wn / _Tgn
(Wherein, Tg is the theoretical glass transition temperature of the resin; Tg ₁ to Tg _n are the glass transition temperatures of the respective homopolymers of the monomers 1, 2, 3, . . . n constituting the copolymer of the resin; W ₁ to W _n represent the respective polymerization fractions of monomers 1, 2, 3, . For the commercially available acrylic resins listed in , the glass transition temperature published by the supplier is not necessarily the theoretical glass transition temperature, but may be considered the theoretical glass transition temperature.

Water-based acrylic resin emulsions include acrylic resin emulsions (made only of acrylic monomers), styrene-acrylic resin emulsions containing styrene-based monomer components, and acrylic-maleic acid resins containing maleic acid monomer components. The emulsion is preferably a styrene-acrylic-maleic acid resin emulsion containing a styrenic monomer component and a maleic acid monomer component.

The water-based acrylic resin emulsion is preferably produced by emulsion polymerization of an ethylenically unsaturated monomer composition in an aqueous solvent using a water-soluble resin (X) having a carboxyl group as a polymer emulsifier. A group-containing aqueous acrylic resin emulsion (Y) is preferred.

The water-soluble resin (X) having a carboxyl group used as a polymer emulsifier has structural units derived from the following monomer components (i) to (iii).
Monomer component (i): carboxylic acid and/or acid anhydride having a radically polymerizable double bond Monomer component (ii): a ketone compound and/or an aldehyde compound having a radically polymerizable double bond (provided that monomer component (ii) is an optional component)
Monomer component (iii): a compound having a radically polymerizable double bond excluding monomer components (i) and (ii)

Examples of monomer component (i) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; esters, monoamides; and acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride. Among these carboxylic acids and/or acid anhydrides having a radically polymerizable double bond, monocarboxylic acids, particularly acrylic acid or methacrylic acid, are preferred from the viewpoint of emulsifying ability as a polymer emulsifier for the water-soluble resin (X). preferred.

The ketone compound having a radically polymerizable double bond of the monomer component (ii) is a radically polymerizable compound having at least one or more keto groups in the molecule, and includes diacetone (meth)acrylamide, diacetone (meth) ) acrylate, acetonyl (meth)acrylate, vinyl alkyl ketones, and the like. The aldehyde compound having a radically polymerizable double bond in the monomer component (ii) is a radically polymerizable compound having at least one or more aldo groups in the molecule, and includes acrolein, formylstyrene, alkanal (meth ) acrylates and the like.

Monomer component (iii) can be, for example, a (meth)acrylic acid derivative, a styrenic compound or a maleic acid derivative described below.
(Meth)acrylic acid derivatives: alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, alkylamides having 1 to 18 carbon atoms, hydroxyalkyl esters having 2 to 4 carbon atoms, etc. specifically, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, methyl ( Meth)acrylamide, ethyl (meth)acrylamide, butyl (meth)acrylamide, hexyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate and the like can be mentioned.
Styrene-based compounds: styrene and its derivatives; specific examples include α-methylstyrene, chlorostyrene, vinyltoluene, and the like.
- Maleic acid derivatives: dialkyl esters of maleic acid having 1 to 18 carbon atoms, dialkylamides having 1 to 18 carbon atoms, dihydroxyalkyl esters having 2 to 4 carbon atoms, etc.; Dimethylmalate, diethylmalate, dibutylmalate, dioctylmalate, bis-2-hydroxyethylmalate, maleic acid dimethylamide, maleic acid diethylamide, maleic acid dibutylamide and the like can be mentioned.

A suitable molecular weight (mass average molecular weight, hereinafter the same) of the water-soluble resin (X) is preferably 3000 or more, more preferably 5000 or less; on the other hand, it is preferably 100000 or less, more preferably 30000 or less. When the molecular weight is 3000 or more, it becomes easy to impart water resistance and blocking resistance to the resulting water-based printing ink composition for surface printing films; The ink composition tends to have a viscosity suitable for printing.

A suitable acid value of the water-soluble resin (X) is preferably 20 mgKOH/g or more, and preferably 300 mgKOH/g or less. When the acid value is 20 mgKOH/g or more, it becomes easy to dissolve in an alkaline aqueous solution; It is easy to obtain printability. The acid value of the water-soluble resin (X) is preferably a theoretical acid value like the acid value of the aqueous acrylic resin emulsion.

The water-soluble resin (X) is obtained by reacting a monomer composition containing monomer components (i) to (iii) in an organic solvent in the presence of a polymerization initiator at a predetermined temperature and reaction time. , can be produced by distilling off the organic solvent.

In the monomer composition to be copolymerized to obtain the water-soluble resin (X), the ratio of the monomer component (i) to the total of the monomer components (i) to (iii) is 2 mass % or more, more preferably 5 mass % or more; on the other hand, it is preferably 50 mass % or less, more preferably 20 mass % or less. The proportion of monomer component (ii) is preferably 0% by mass or more, more preferably 1% by mass or more, relative to the total of monomer components (i) to (iii); % by mass or less, more preferably 4% by mass or less. The ratio of the monomer component (iii) is preferably 50 to 98% by mass with respect to the total of the monomer components (i) to (iii).

In the monomer composition to be copolymerized to obtain the water-soluble resin (X), when the ratio of the monomer component (i) is 2% by mass or more, the resulting aqueous alkaline solution of the water-soluble resin (X) Sufficient solubility in water is obtained. Therefore, the stability of the emulsion polymerization and the dispersion stability of the polymer can be obtained, and as a result, the fluidity of the water-based printing ink composition for surface printing film is improved. On the other hand, when the proportion of the monomer component (i) is 50% by mass or less, the printability of the resulting ink composition containing the resin emulsion is improved, and the water resistance of the printed layer is enhanced. In the monomer composition to be copolymerized, when the proportion of the monomer component (ii) is 5% by mass or less, the resulting water-based printing ink composition for surface printing film containing the resin emulsion is stable over time. is improved, thickening and solidification can be prevented, and deterioration of printability can be suppressed.

Examples of organic solvents for copolymerizing the monomer composition containing monomer components (i) to (iii) include esters such as ethyl acetate and isopropyl acetate; ketones such as acetone and methyl ethyl ketone; Alcohols, glycols and derivatives thereof and the like are included.

Examples of polymerization initiators for copolymerizing the monomer composition containing monomer components (i) to (iii) include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate; Organic peroxides such as peroxides, azo compounds such as azobisisobutyronitrile, and, if necessary, redox initiators combined with reducing agents can be mentioned.

The acid group-containing aqueous acrylic resin emulsion (Y) can be obtained by emulsion polymerization of an ethylenically unsaturated monomer composition in an aqueous solvent using the water-soluble resin (X) as a polymer emulsifier. Preferably, after dissolving the water-soluble resin (X) in an alkaline aqueous solution, a mixture of an ethylenically unsaturated monomer composition and a polymerization initiator is added dropwise, and ethylenically unsaturated monomers are added at a predetermined temperature and reaction time. It can be produced by polymerizing a monomer. In the resin emulsion thus obtained, the resin solid content is usually 20 to 60% by mass.

The resulting acid group-containing water-based acrylic resin emulsion (Y) is not particularly limited, but may have a core-shell type in which the core is composed of a copolymer of an ethylenically unsaturated monomer composition, and the shell The part may be composed of the component of the water-soluble resin (X).

The ethylenically unsaturated monomer composition to be emulsion-polymerized contains the monomer component (iv), "a ketone and/or aldehyde compound having a radically polymerizable double bond" (monomer component (iv) is used as necessary) and the monomer component (v), which is "a compound having a radically polymerizable double bond, excluding component (iv)".

Examples of monomeric component (iv) include the ketone and aldehyde compounds having radically polymerizable double bonds mentioned as monomeric component (ii).

Examples of monomer component (v) include carboxylic acids and/or acid anhydrides having radically polymerizable double bonds mentioned as monomer component (i); meth)acrylic acid derivatives, styrene compounds, maleic acid derivatives; vinyl esters of saturated carboxylic acids having 2 to 18 carbon atoms, specifically vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, etc. can be mentioned. Suitable examples of the monomer component (v) include (meth)acrylic acid derivatives and styrenic compounds; To improve the performance of aqueous printing ink compositions for surface printing films.

In the ethylenically unsaturated monomer composition to be emulsion polymerized, the ratio of the monomer component (iv) to the total of the monomer component (iv) and the monomer component (v) is 0 to 30% by mass. The ratio of the monomer component (v) is preferably 70 to 100% by mass. When the ratio of the monomer component (iv) is 30% by mass or less, the resulting printing ink composition containing the resin emulsion has good stability over time, prevents thickening and solidification, and lowers printability. can be suppressed.

In the obtained acid group-containing water-based acrylic resin emulsion (Y), the ratio of the total mass of monomer components (ii) and (iv) to the total mass of monomer components (i) to (v) is preferably 0.5 to 25% by mass. When the total mass ratio of the monomer component (ii) and the monomer component (iv) is 0.5% by mass or more, sufficient adhesion of the resulting resin emulsion-containing printing ink to a plastic film can be obtained. Cheap.

In the production of the acid group-containing water-based acrylic resin emulsion (Y), the water-soluble resin (X) relative to the total mass of the monomer components (iv) and (v) contained in the ethylenically unsaturated monomer composition The mass ratio of "(X)/(iv)+(v)" ranges from 20/80 to 80/20, preferably from 30/70 to 70/30. Here, when the ratio is 20/80 or more, the resolubility, fluidity, and storage stability of the printing ink containing the resulting resin emulsion are likely to increase, and when the ratio is 80/20 or less, the water resistance of the printed layer, etc. is easy to secure.

In the production of the acid group-containing water-based acrylic resin emulsion (Y), the alkaline aqueous solution for dissolving the water-soluble resin (X) preferably contains an alkaline substance (preferably a volatile basic compound) described later. The appropriate amount of alkaline substance used is about 100 to 120% of the amount required to completely neutralize the water-soluble resin (X). Sufficient water affinity of emulsion (Y) is obtained; on the other hand, more than 120% does not further increase the water affinity of resin emulsion (Y)

Examples of the polymerization initiator used in the emulsion polymerization in the production of the acid group-containing water-based acrylic resin emulsion (Y) include the polymerization initiators shown in the production of the water-soluble resin (X) described above.

Aqueous acrylic resins are also commercially available. Commercially available products include, for example, Seiko PMC's trade name "X-436"; Aica Kogyo Co., Ltd.'s trade names "Ultrasol A-35" and "Ultrasol KJ-1"; BASF Japan Co., Ltd.'s trade name " Joncryl PDX-7356” and “Joncryl PDX-7696”.

[1-1-1-2. Water-based urethane resin emulsion]
The water-based urethane-based resin emulsion refers to a resin liquid in which the water-based urethane-based resin is emulsified and stabilized in the form of particles. The water-based urethane-based resin emulsion is preferably an emulsion of a polyester-based, polyether-based or polycarbonate-based water-based urethane-based resin. Polyester-based, polyether-based, and polycarbonate-based resins refer to water-based urethane-based resins whose main raw materials for synthesizing the water-based urethane-based resin are polyester polyol, polyether polyol, and polycarbonate polyol, respectively.

The water-based urethane resin has an acid value, and the acid value is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more; on the other hand, it is preferably 60 mgKOH/g or less, more preferably 50 mg KOH/g. Moreover, the hydroxyl value of the water-based urethane resin is preferably 1 mgKOH/g or more; on the other hand, it is preferably 35 mgKOH/g, more preferably 25 mgKOH/g or less. The acid value of the water-based urethane resin can be calculated as a theoretical acid value in the same manner as the acid value of the water-based acrylic resin emulsion.

The glass transition temperature of the aqueous urethane resin is preferably −90° C. or higher, more preferably −80° C. or higher, and still more preferably −70° C. or higher; on the other hand, it is preferably 140° C. or lower, More preferably, it is 120° C. or less. This is for enhancing the substrate adhesion of the resulting printed layer. Here, the glass transition temperature means a value measured by differential scanning calorimetry (DSC) or a value measured by dynamic mechanical measurement (DMA).

The weight average molecular weight of the aqueous urethane resin is preferably 1×10 ⁴ to 1×10 ⁵ , more preferably 2×10 ⁴ to 7×10 ⁴ . The mass average molecular weight of the water-based urethane resin can be measured by gel permeation chromatography (GPC). For example, chromatography is performed using Water 2690 (Waters, Inc.) as a GPC device and PLgel 5 μ MIXED-D (Polymer Laboratories, Inc.) as a column, and the weight average molecular weight can be obtained in terms of polystyrene.

The aqueous urethane resin can be produced, for example, according to the methods described in JP-A-2008-1911 and JP-A-2017-8292. Aqueous urethane resins are obtained by reacting high-molecular-weight polyols (e.g., polyether polyols and/or polyester polyols) with polyisocyanates, and further include low-molecular-weight diols, low-molecular-weight compounds having 3 or more hydroxyl groups, dihydroxy acids, and the like. is preferably reacted as a raw material. Furthermore, the water-based urethane-based resin may be chain-extended using a polyamine.

The number average molecular weight of structural units derived from polymeric polyols (polyether polyols, polyester polyols, and other polyols) constituting the water-based urethane resin is preferably 500 to 7,000, more preferably 1,000 to 5,000.

The water-based urethane resin may have structural units derived from polyether polyol; the polyether polyol is preferably polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer polyether polyol, polytetramethylene glycol, or the like. can be Among them, the aqueous urethane resin preferably has a structural unit derived from polyethylene glycol, and the content thereof is preferably 1 to 35% by mass, preferably 2 to 30% by mass, based on the total mass of the aqueous urethane resin. more preferably 2 to 25% by mass. When the water-based urethane-based resin contains the polyethylene glycol-derived structural unit within the above range, poor printing is less likely to occur.

The water-based urethane resin may have structural units derived from polyester polyol; however, the polyester polyol is preferably a condensate of a low-molecular-weight diol and a dibasic acid. Low-molecular-weight diols include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 2-methyl- 1,3-propanediol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1 ,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2 A low-molecular-weight diol having a branched structure such as ,4-trimethyl-1,6-hexanediol is preferred. A low-molecular-weight diol having a branched structure refers to a diol having a structure in which at least one hydrogen atom of an alkylene group of the diol is substituted with an alkyl group. Dibasic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and trimellitic acid. Acids, polyvalent carboxylic acids such as pyromellitic acid, and anhydrides thereof are preferred. Among them, the dibasic acid is preferably adipic acid, sebacic acid, aceraic acid, succinic acid or other aliphatic dibasic acids.

Aqueous urethane-based resins have structural units derived from polyisocyanates; Alicyclic diisocyanates are preferred.

Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and 1,3-phenylene diisocyanate. , 1,4-phenylene diisocyanate, tolylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate-benzyl chloride.

Examples of 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, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, Examples include methylcyclohexane diisocyanate, norbornane diisocyanate, and dimer diisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.

The water-based urethane resin may have a structural unit derived from a low-molecular-weight diol; examples of the low-molecular-weight diol include the diols exemplified as the low-molecular-weight diols constituting the polyester polyol, and 1,4-cyclohexanedimethanol. , 1,4-cyclohexanediol and other diols having an aliphatic ring structure.

Aqueous urethane-based resins may have structural units derived from low-molecular-weight compounds having 3 or more hydroxyl groups: Examples of low-molecular-weight compounds having 3 or more hydroxyl groups include trimethylolethane, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol and the like, but trimethylolpropane is more preferred. The water-based urethane-based resin preferably contains 0.1 to 0.8% by mass of structural units derived from a low-molecular-weight compound having 3 or more hydroxyl groups with respect to the entire resin. This is for improving the hardness of the printed ink film.

Aqueous urethane resins may have structural units derived from dihydroxy acids; the dihydroxy acids include, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like. dimethylolalkanoic acid; diamine-type amino acids such as glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, and diaminobenzenesulfonic acid, but water-based urethane resins are structural units derived from dimethylolalkanoic acid It is preferred to have The water-based urethane-based resin may have these structural units singly or in combination of two or more. In the synthesis of urethane-based resins, the carboxyl group contained in each resin raw material remains without being decomposed under mild synthetic reaction conditions of 50 to 140°C.

Some or all of the acid groups contained in the water-based urethane resin (for example, acid groups of structural units derived from dimethylolalkanoic acid or dihydroxy acid) may be neutralized with a basic compound. However, depending on the degree of neutralization, the water solubility of the resin increases and the resin emulsion cannot be formed (the resin dissolves). Therefore, the degree of neutralization is adjusted so that the resin emulsion can be formed. Basic compounds used for neutralization include ammonia, monoethylamine, diethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N Amine compounds such as -methylmorpholine and 2-amino-2-methyl-1-propanol; inorganic oxides such as sodium hydroxide and potassium hydroxide;

The water-based urethane-based resin may be chain-extended using a polyamine; Organic diamines containing hydroxyl groups such as ethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and further Organic diamines containing no hydroxyl group such as dimer diamine obtained by converting the carboxyl group of a dimer acid to an amino group can be mentioned.

Water-based urethane resins are also commercially available. Commercially available products include, for example, DIC Corporation's trade name "Hydran WLS-210"; Nicca Chemical Co., Ltd.'s trade names "Neo Sticker 400" and "Neo Sticker 200"; Flex 500M”; Trade names of Mitsui Chemicals, Inc. “Takelac W-5010”, “Takelac W-6010”, “Takelac W-6110”, “Takelac WA-4000”, “Takelac W-635”, “Takelac W- 5100”.

[1-1-1-3. Water-based acrylic urethane resin emulsion]
The water-based urethane acrylic resin emulsion refers to a resin liquid in which the water-based urethane acrylic resin is stabilized in the form of particles. The water-based urethane-acrylic resin is a resin containing a urethane resin portion and an acrylic resin portion. The resin containing the urethane resin portion and the acrylic resin portion may be an alternating copolymer of urethane units and acrylic units; Alternatively; a urethane resin may be bonded as a side chain to the acrylic resin constituting the main chain. The water-based acrylic urethane resin can be produced, for example, by referring to the methods described in JP-A-4-103614, JP-A-10-139839, and the like.

The water-based acrylic urethane resin preferably has acid groups, and may be rendered water-based by neutralizing the acid groups. In other words, an acid group may be introduced into the acrylic resin portion of the aqueous acrylic urethane resin, or an acid group may be introduced into the urethane resin portion. As described above, introduction of acid groups into the acrylic resin portion is possible by using a carboxylic acid and/or an acid anhydride having a radically polymerizable double bond as a polymer component, but is not particularly limited. As described above, introduction of acid groups into the urethane-based resin portion is possible by using dimethylolalkanoic acid or dihydroxy acid as a resin raw material, but is not particularly limited.

The acid value of the aqueous acrylic urethane resin is preferably 5 mgKOH/g or more, more preferably 25 mgKOH/g or more, still more preferably 30 mgKOH/g or more; preferably 100 mgKOH/g or less, It is more preferably 80 mgKOH/g or less, still more preferably 60 mgKOH/g or less. The acid value of the water-based acrylic urethane resin can be calculated as a theoretical acid value in the same manner as for the water-based acrylic resin.

The weight average molecular weight of the aqueous acrylic urethane resin is preferably 1×10 ⁴ to 12×10 ⁴ , more preferably 2×10 ⁴ to 8×10 ⁴ . The weight average molecular weight of the aqueous acrylic urethane resin can be measured by gel permeation chromatography (GPC). For example, chromatography is performed using Water 2690 (Waters, Inc.) as a GPC device and PLgel 5 μ MIXED-D (Polymer Laboratories, Inc.) as a column, and the weight average molecular weight can be obtained in terms of polystyrene.

The mass ratio of the urethane resin portion to the acrylic resin portion (urethane resin portion:acrylic resin portion) of the water-based acrylic urethane resin is preferably in the range of 90:10 to 30:70. When the acrylic resin portion in the water-based acrylic urethane resin is 10% by mass or more, it is easy to impart sufficient water resistance to the printed layer, and when the acrylic resin portion is 70% by mass or less, the printed layer adheres sufficiently to the plastic substrate. It is easy to impart properties, and the anti-blocking property is also improved.

The glass transition temperature of the acrylic resin portion of the aqueous acrylic urethane resin is preferably −10° C. or higher, more preferably 40° C. or higher, and still more preferably 60° C. or higher; on the other hand, it should be 110° C. or lower. is preferred. The glass transition temperature of the acrylic resin portion can be calculated as a theoretical glass transition temperature determined by Wood's formula in the same manner as for the water-based acrylic resin.

The urethane resin part in the water-based acrylic urethane-based resin may have a structural unit composed of the same raw material as the water-based urethane-based resin described above. The mass ratio of structural units derived from polyether polyol and/or polyester polyol is preferably 50% by mass, more preferably 60% by mass or more, relative to the total mass of the urethane resin portion.

On the other hand, the acrylic resin part in the water-based acrylic urethane resin has structural units derived from acrylic monomers. Examples of acrylic monomers include aromatic alkyl group-containing acrylic monomers, linear or branched alkyl group-containing acrylic monomers, alicyclic alkyl group-containing acrylic monomers, fluorinated alkyl group-containing acrylic monomers, amide group-containing acrylic monomers, hydroxyl Group-containing acrylic monomers, polyethylene oxide group-containing acrylic monomers, and the like are included.

Examples of aromatic alkyl group-containing acrylic monomers include benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol acrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene. Glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenyl acrylate, phenyl methacrylate and the like are included.

Examples of linear or branched alkyl group-containing acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl ( meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl ( meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate and the like are included.

Examples of alicyclic alkyl group-containing acrylic monomers include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and the like. Examples of fluorinated alkyl group-containing acrylic monomers include trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and the like.

Examples of amide group-containing acrylic monomers include (meth)acrylamide, N-methoxymethyl-(meth)acrylamide, N-ethoxymethyl-(meth)acrylamide, N-propoxymethyl-(meth)acrylamide, N-butoxymethyl- (meth)acrylamide, N-pentoxymethyl-(meth)acrylamide, N,N-di(methoxymethyl)acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N,N-di(ethoxymethyl)acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N,N-di(propoxymethyl)acrylamide, N-butoxymethyl-N-(propoxymethyl)methacrylamide, N,N-di(butoxymethyl)acrylamide, N- butoxymethyl-N-(methoxymethyl)methacrylamide, N,N-di(pentoxymethyl)acrylamide, N-methoxymethyl-N-(pentoxymethyl)methacrylamide, N,N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide and the like are included.

Examples of hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl alcohol and the like are included.

Examples of polyethylene oxide group-containing acrylic monomers include polyethylene glycol monoacrylate (NOF Co., Ltd., Blenmer PE-90, 200, 350, 350G, AE-90, 200, 400, etc.), polyethylene glycol/polypropylene glycol monoacrylate (Japan Brenmer 50PEP-300, 70PEP-350, etc., manufactured by Yushi Co., Ltd.), methoxypolyethylene glycol monoacrylate (Nippon Oil Co., Ltd., Blenmer PME-400, 550, 1000, 4000, etc.).

The acrylic resin portion of the aqueous acrylic urethane resin preferably has structural units derived from monomers other than acrylic monomers; preferred examples of monomers other than acrylic monomers include styrene, α-methylstyrene, o-methylstyrene, p Aromatic monomers such as -methylstyrene, m-methylstyrene and vinylnaphthalene are included.

The aqueous acrylic urethane resin can be produced, for example, by the following procedure: 1) Polyol, polyisocyanate, and optionally dimethylolalkanoic acid are polymerized in an organic solvent to produce a urethane resin (α). 2) After neutralizing the urethane resin (α) with a basic compound, 3) after replacing the solvent with water, an acrylic monomer is added and radical polymerization (especially Although not limited, it may be graft polymerization) to form an acrylic resin part, and an emulsion of the water-based acrylic urethane resin (β) can be obtained.

It is considered that an emulsion of the aqueous acrylic urethane resin (β) can be obtained by graft polymerizing the acrylic monomer with the urethane resin (α). Although not particularly limited, the graft polymerization of acrylic monomers proceeds by abstraction reaction of hydrogen atoms of alkylene groups contained in structural units derived from polyester polyols, polyether polyols and other polyols in the urethane resin (α). However, it is not particularly limited.

A known organic peroxide can be used as the organic peroxide (radical polymerization initiator) for radically polymerizing the acrylic monomer. Examples of organic peroxides include benzoyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxy-3,5 ,5-trimethylhexanoate, di-t-butyl peroxide and the like.

The reaction temperature in the acrylic monomer polymerization reaction is preferably 40 to 140° C., and the reaction time is preferably about 30 minutes to 10 hours, but is not particularly limited.

The acidic group of the water-based acrylic urethane resin (β) may be neutralized with a basic compound to render it water-based. Examples of applicable basic compounds include those exemplified for urethane-based resins. Among them, amine compounds are preferred, and use of ammonia is preferred.

Aqueous acrylic urethane resins are also commercially available. Commercially available products include, for example, trade names “WEM-200U”, “WEM-505C” and “WEM-3000” manufactured by Taisei Fine Chemical Co., Ltd.

[1-1-2. Water-soluble resin]
The water-soluble resin contained in the water-based printing ink composition of the present invention is usually a water-soluble acrylic resin. A water-soluble acrylic resin may be used to disperse the pigment. Therefore, when the water-based printing ink composition does not contain a pigment, it may not contain a water-soluble resin (water-soluble acrylic resin) either.

The monomer components constituting the water-soluble acrylic resin include a monomer having a carboxyl group, a monomer containing a hydrophobic group for improving adsorption to pigments, and other polymerizable monomers. consists of the body and The water-soluble acrylic resin is an alkali-soluble resin in which part or all of the carboxyl groups in the monomer units having carboxyl groups constituting it are neutralized with a basic compound (preferably a volatile basic compound). preferably used.

Examples of monomers having carboxyl groups that constitute water-soluble acrylic resins include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth)acrylate, and 2-carboxypropyl. (Meth)acrylates, maleic anhydride, maleic acid monoalkyl esters, citraconic acid, citraconic anhydride, citraconic acid monoalkyl esters and the like are included.

Preferred examples of the monomer containing a hydrophobic group for improving adsorptivity with the pigment constituting the water-soluble acrylic resin include (meth)acrylates having a long-chain alkyl group with 6 to 20 carbon atoms. Among them, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxystearyl (meth)acrylate and the like are more preferable; Styrene, α-styrene, vinyltoluene, etc. can be used as the carrier.

Other polymerizable monomers constituting the water-soluble acrylic resin can be used as long as they do not impair the properties of the water-soluble acrylic resin. (Meth) acrylic acid such as propyl acid, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylamide, N-methylolacrylamide, cyclohexyl (meth) Acrylate, benzyl (meth)acrylate and the like can be used.

Volatile basic compounds for neutralizing water-soluble acrylic resins (neutralizing some or all of the carboxyl groups in monomer units having carboxyl groups) include ammonia, triethylamine, and N,N-dimethylethanolamine. , monoethanolamine, etc., among which ammonia is preferred. Inorganic alkali compounds such as sodium hydroxide and potassium hydroxide, and non-volatile amine compounds such as triethylenediamine, diethanolamine, triethanolamine, diethylenetriamine, and diazabicyclooctane can also be used in combination, as long as the performance does not deteriorate.

The acid value of the water-soluble acrylic resin is preferably 40 mgKOH/g or more, more preferably 70 mgKOH/g or more; on the other hand, it is preferably 250 mgKOH/g or less. When the acid value of the alkali-soluble resin is 40 mgKOH/g or more, sufficient solubility of the aqueous printing ink composition in an aqueous solvent can be obtained. On the other hand, when the acid value is 250 mgKOH/g or less, the hydrophilicity of the water-based printing ink composition is moderate, the storage stability is enhanced, and water resistance is easily imparted to the printed layer. The acid value of the water-soluble acrylic resin is preferably a theoretical acid value like the acid value of the water-soluble acrylic resin emulsion.

[1-2. Acyl taurinate and/or acyl amino acid salt]
The water-based printing ink composition of the present invention contains acyl taurinate and/or acyl amino acid salt having a specific acyl group. Acyl taurate is a compound in which the amino group of tauric acid (also called "taurine") (HN( _R2 )-CH2CH2 _{- SO2OH} ) is acylated and the sulfonyl group of tauric acid is salted. is. An acyl amino acid salt is a compound in which the amino group of an amino acid (HN(R4)-CH(R5)-COOH) is acylated and the carboxyl group of the amino acid is a salt. The acyl group preferably has 10 to 20 carbon atoms, more preferably 16 to 20 carbon atoms.

[1-2-1. Acyl taurinate]
The acyl taurate contained in the water-based printing ink composition of the present invention can be represented by (Formula I) below. In (Formula I), R1-C(=O)- represents an acyl group; R2 represents a hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group, n-propyl group, iso-propyl group). , M indicates the counterion for sulfonic acid.

In (Formula I), the carbon number of R1-C(=O)- representing an acyl group is in the range of 10-20, that is, the carbon number of R1 is in the range of 9-19. R1 is any hydrocarbon group (optionally substituted), but: linear, branched or cyclic alkyl group (saturated hydrocarbon group); linear, branched or cyclic alkenyl groups (hydrocarbon groups with one or more unsaturated carbon-carbon double bonds); linear, branched or cyclic alkynyl groups (hydrocarbon groups with one or more unsaturated carbon-carbon triple bonds ); or an aromatic hydrocarbon group. R1 is preferably a linear, branched or cyclic alkyl group, or a linear, branched or cyclic alkenyl group; more preferably a linear or branched alkyl group, or a linear or branched It is a chain alkenyl group.

The acyl group (R1-C(=O)-) in (Formula I) has 10 to 20 carbon atoms (that is, R1 has 9 to 19 carbon atoms), preferably 16 to 20 (that is, R1 has carbon atoms The numbers are 15-19). When the number of carbon atoms in the acyl group is 10 or more, the anti-blocking property of the printed layer of the obtained water-based printing ink composition is enhanced.

Preferred examples of the acyl group (R1-C(=O)-) in (Formula I) include a decanoyl group (caprinoyl group (C10)), an undecanoyl group (C11), a dodecanoyl group (lauroyl group (C12)), tridecanoyl group (C13), tetradecanoyl group (myristoyl group C14), pentadecanoyl group (C15), hexadecanoyl group (palmitoyl group (C16)), heptadecanoyl group (C17), octadecanoyl group (stearoyl group (C18 )), a nonadecanoyl group (C19), an acyl group having an alkyl group such as an icosanoyl group (C20); an oleoyl group (C18), a linoleoyl group (C18), an acyl group having an alkenyl group such as a linolenoyl group (C18); A combination of multiple kinds of fatty acid acyl groups such as a cocoyl group (coconut oil fatty acid acyl group);

R2 in (Formula I) is a hydrogen atom or a lower alkyl group. Examples of lower alkyl groups include methyl, ethyl, n-propyl, iso-propyl, and the like. R2 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

M in (Formula I) represents a counter ion for sulfonic acid; preferably an alkali ion, ammonium ion or an organic aminium ion. That is, the acyl taurate may be alkali salts, ammonium salts, organic amine salts, and the like. Examples of alkaline ions include lithium ions, sodium ions, potassium ions, and the like.

Specific examples of acyl taurate salts include sodium lauroyl methyl taurate, potassium lauroyl methyl taurate, ammonium lauroyl methyl taurate; sodium myristoyl methyl taurate, potassium myristoyl methyl taurate, ammonium myristoyl methyl taurate; sodium palmitoyl methyl taurate, potassium palmitoyl methyl taurate, ammonium palmitoyl methyl taurate; sodium stearoyl methyl taurate; sodium cocoyl methyl taurate, potassium cocoyl methyl taurate, ammonium cocoyl methyl taurate, sodium cocoyl taurate; sodium oleoyl methyl taurate;

[1-2-2. Acyl amino acid salt]
The acyl amino acid salt contained in the water-based printing ink composition of the present invention can be represented by (Formula II) below. In (Formula II), R3-C(=O)- represents an acyl group; R4 represents a hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group, n-propyl group, iso-propyl group). R5 represents a hydrogen atom or a lower alkyl group (which may have a hydroxyl group, a carboxyl group or a sulfhydryl group); M represents a counterion to the carboxylic acid.

In (Formula II), the carbon number of R3-C(=O)- representing an acyl group is in the range of 10-20, that is, the carbon number of R3 is in the range of 9-19. R3 is any hydrocarbon group (optionally substituted) with: straight, branched or cyclic alkyl group (saturated hydrocarbon group); straight, branched or cyclic alkenyl groups (hydrocarbon groups with one or more unsaturated carbon-carbon double bonds); linear, branched or cyclic alkynyl groups (hydrocarbon groups with one or more unsaturated carbon-carbon triple bonds ); or an aromatic hydrocarbon group. R3 is preferably a linear, branched or cyclic alkyl group, or a linear, branched or cyclic alkenyl group; more preferably a linear or branched alkyl group, or a linear or branched It is a chain alkenyl group.

The acyl group (R3-C(=O)-) in (Formula II) has 10 to 20 carbon atoms (that is, R3 has 9 to 19 carbon atoms), preferably 16 to 20 (that is, R3 has carbon atoms The numbers are 15-19). When the number of carbon atoms in the acyl group is 10 or more, the anti-blocking property of the printed layer of the obtained water-based printing ink composition is enhanced.

Preferred examples of the acyl group (R3-C(=O)-) in (Formula II) include a decanoyl group (caprinoyl group (C10)), an undecanoyl group (C11), a dodecanoyl group (lauroyl group (C12)), tridecanoyl group (C13), tetradecanoyl group (myristoyl group C14), pentadecanoyl group (C15), hexadecanoyl group (palmitoyl group (C16)), heptadecanoyl group (C17), octadecanoyl group (capryloyl group (C18 )), a nonadecanoyl group (C19), an acyl group having an alkyl group such as an icosanoyl group (C20); an oleoyl group (C18), a linoleoyl group (C18), an acyl group having an alkenyl group such as a linolenoyl group (C18); A combination of multiple kinds of fatty acid acyl groups such as a cocoyl group (coconut oil fatty acid acyl group);

R4 in (Formula II) is a hydrogen atom or a lower alkyl group. Examples of lower alkyl groups include methyl, ethyl, n-propyl, iso-propyl, and the like. R4 is preferably a hydrogen atom or a methyl group.

M in (Formula II) represents a counter ion for carboxylic acid; preferably an alkali ion, an ammonium ion or an organic aminium ion. Thus, acyl amino acid salts can be alkali salts, ammonium salts, organic amine salts, and the like. Examples of alkaline ions include lithium ions, sodium ions, potassium ions, and the like. Examples of organic aminium ions include triethanolaminium ions.

R5 represents a hydrogen atom or a lower alkyl group. In addition, the lower alkyl group of R5 may have a hydroxy group, a carboxyl group, or a sulfhydryl group (thiol group). Alkyl groups for R5 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, hydroxymethyl group and carboxymethyl group. , a sulfhydrylmethyl group, a hydroxyethyl group, a carboxyethyl group, and the like.

That is, examples of the amino acid (HN(R4)-CH(R5)-COOH) of the acylamino acid salt represented by (Formula II) include glycine (R4 = hydrogen atom, R5 = hydrogen atom), alanine (R4 = hydrogen atom, R5 = methyl group), sarcosine (R4 = methyl group, R5 = hydrogen atom), threonine (R4 = hydrogen atom, R5 = 1-hydroxyethyl group), glutamic acid (R4 = hydrogen atom, R5 = carboxyethyl group), Aspartic acid (R4 = hydrogen atom, R5 = carboxymethyl group), serine (R4 = hydrogen atom, R5 = hydroxymethyl group), leucine (R4 = hydrogen atom, R5 = iso-butyl group), cysteine (R4 = hydrogen atom , R5=sulfhydrylmethyl group), valine (R4=hydrogen atom, R5=iso-propyl group) and the like.

Specific examples of acylamino acid salts represented by formula II include sodium lauroyl aspartate, potassium lauroyl aspartate, sodium lauroyl glutamate, potassium lauroyl glutamate, triethanolamine lauroyl glutamate, sodium lauroyl sarcosine, potassium lauroyl sarcosine, and lauroyl sarcosine. Triethanolamine, sodium lauroyl threonine, sodium lauroyl methyl alanine, triethanolamine lauroyl methyl alanine; sodium myristoyl glutamate, potassium myristoyl glutamate, sodium myristoyl sarcosine, sodium myristoyl methyl alanine; triethanolamine palmitoyl aspartate; sodium stearoyl glutamate, stearoyl glutamic acid Potassium, Salts of Stearoylleucine; Cocoyl Alanine Triethanolamine, Sodium Cocoyl Glycinate, Potassium Cocoyl Glycine, Cocoyl Glycine Triethanolamine, Sodium Cocoyl Glutamate, Potassium Cocoyl Glutamate, Triethanolamine Cocoyl Glutamate, Sodium Cocoyl Sarcosinate, Potassium Cocoyl Sarcosine, Cocoyl sarcosine triethanolamine, sodium cocoylmethylalanine, potassium cocoylmethylalanine; salts of oleoyl sarcosine, and the like.

[1-2-3. Content of acyl taurinate and/or acyl amino acid salt]
The water-based printing ink composition of the present invention contains a total of 0.3% by mass or more, preferably 0.5% by mass, of acyl taurinate and/or acylamino acid salt having an acyl group having 10 to 20 carbon atoms. or more, more preferably 0.7% by mass or more, particularly preferably 1.0% by mass or more; on the other hand, the total content is 10.0% by mass or less, preferably 7.0% by mass or less Yes, more preferably 5.0% by mass or less. When the total content of the acyl taurinate and/or acyl amino acid salt having an acyl group having 10 to 20 carbon atoms is 0.3% by mass or more, sufficient blocking resistance can be imparted to the printed layer; When the amount is 0% by mass or less, sufficient water resistance and trapping properties can be imparted to the printed layer, and defoaming properties of the ink composition can also be obtained.

[1-3. Aqueous medium]
The aqueous printing ink composition of the present invention contains an aqueous medium consisting of water or an aqueous medium consisting of a mixed solvent of water and a water-soluble organic solvent. In the water-based printing ink composition of the present invention, the content of the water-soluble organic solvent mixed with water is preferably as low as possible, and may not be added; A range of to 10.0% by mass is preferable, and a range of 0 to 5.0% by mass is more preferable. If it exceeds 10.0% by mass, poor drying and anti-blocking properties will decrease.

Examples of water-soluble organic solvents used as aqueous media by mixing with water include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, nitrogen-containing Compounds etc. can be mentioned. These may be used alone or in combination of two or more.

Examples of monoalcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or These isomers, cyclopentanol, cyclohexanol and the like can be mentioned, and alcohols having an alkyl group of 1 to 6 carbon atoms can be preferably used.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2 -hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol and the like.

Examples of lower alkyl ethers of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol isobutyl. Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- n-butyl ether and the like can be used.

[1-4. Pigment]
The aqueous printing ink composition of the present invention may or may not contain a pigment. In other words, when the water-based printing ink composition is used as a colored ink, a pigment is blended; A pigment may be contained within a range that does not reduce the

Pigments that can be contained in the water-based printing ink composition of the present invention include various inorganic pigments and/or organic pigments commonly used in printing inks. Inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite, silica, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, talc, and the like. Extender pigments can be mentioned. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.

The content of the pigment in the water-based printing ink composition of the present invention may be 0 as described above; Weight percent ranges are preferred. When the content of the pigment in the water-based color printing ink composition for surface printing film is less than the above range, the coloring power of the water-based color printing ink composition for surface printing film decreases, and when it exceeds the above range, the surface The viscosity of the water-based printing color ink composition for printed film becomes high, and the printed matter becomes easily smeared.

[1-5. Phosphate ester surfactant]
The water-based printing ink composition of the present invention may contain a phosphate surfactant. Phosphate ester surfactants preferably have the formula: RO-P(=O)(OH) ₂ , RO-P(=O)(OH)(OM), RO-P(=O)(OM) ₂ , a phosphate _ester or a _salt thereof; _n- , R'=alkyl, phenyl, etc.) or a salt thereof. Phosphate ester salts are typically alkali salts (sodium salts and potassium salts) and organic amine salts (monoethanolamine salts).

Specific examples of phosphate surfactants include Plysurf (registered trademark, Daiichi Kogyo Seiyaku) AL (polyoxyethylene styrenated phenyl ether phosphate), Plysurf DB-01 (polyoxyethylene lauryl ether acid ester/monoethanolamine salt), Plysurf A219B (polyoxyethylene lauryl ether phosphate), Plysurf A208B (polyoxyethylene lauryl ether phosphate), Plysurf 212C (polyoxyethylene tridecyl ether phosphate) ), etc.

The content of the phosphate ester surfactant in the water-based printing ink composition of the present invention is preferably 0.1% by mass, more preferably 0.3% by mass or more; % by mass or less, more preferably 0.7% by mass or less. When the content of the phosphate ester-based surfactant is 0.1% by mass or more, the heat resistance of the printed layer formed from the water-based printing ink composition is increased, and the heat seal resistance is improved. When the content of the phosphate ester-based surfactant is 1.0% by mass or less, the water resistance and trapping properties of the printed layer formed from the water-based printing ink composition are enhanced.

[1-6. Crosslinking agent]
The aqueous printing ink composition of the present invention may further contain a cross-linking agent. The cross-linking agent is preferably capable of cross-linking the water-based binder resin contained in the water-based printing ink composition in the formed print layer. Examples of cross-linking agents include epoxy-based curing agents, aziridine-based curing agents, hydrazine compounds, carbodiimide compounds, and the like.

Examples of epoxy-based curing agents include fatty acids such as glycerol polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like. and polyglycidyl ethers of group polyhydric alcohols.

Examples of aziridine-based curing agents are not particularly limited as long as they are compounds containing at least two aziridine groups (aziridinyl groups) in the molecule. For example, trimethylolpropane-tris[3-(1-aziridinyl) propionate], trimethylolpropane-tris[3-(1-aziridinyl)butyrate], trimethylolpropane-tris[3-(1-(2-methyl)aziridinyl)propionate], trimethylolpropane-tris[3-(1 -aziridinyl)-2-methylpropionate], pentaerythritol-tris[3-(1-aziridinyl)propionate], pentaerythritol-tetra[3-(1-aziridinyl)propionate], tris(1-(2-methyl ) aziridinyl)phosphine oxide, tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, ethylene glycol-bis[3-(1-aziridinyl)propionate], polyethylene glycol-bis[3 -(1-aziridinyl)propionate], propylene glycol-bis[3-(1-aziridinyl)propionate], polypropyleneglycol-bis[3-(1-aziridinyl)propionate], tetramethylene glycol-bis[3-(1- aziridinyl)propionate], polytetramethylene glycol-bis[3-(1-aziridinyl)propionate], N,N'-tetramethylenebisethyleneurea, N,N'-hexamethylenebisethyleneurea, N,N'-phenylene Bisethyleneurea, N,N'-toluylenebisethyleneurea, N,N'-diphenyl-4,4'-bisethyleneurea, 3,3'-dimethyldiphenyl-4,4'-bisethyleneurea, diphenylmethane P .P-bisethylene urea, N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), bis[1-(2-ethyl)aziridinyl]benzene-1,3-carboxylic acid amide, etc. These can be used alone or in combination of two or more. Among these, trimethylolpropane-tris[3-(1-aziridinyl)propionate], trimethylolpropane-tris[3-(1-aziridinyl)butyrate], trimethylolpropane-tris[3-(1-(2- methyl)aziridinyl)propionate], trimethylolpropane-tris[3-(1-aziridinyl)-2-methylpropionate], pentaerythritol-tris[3-(1-aziridinyl)propionate], pentaerythritol-tetra[3 A polyaziridine having three or more aziridinyl groups such as -(1-aziridinyl)propionate] is preferably used. Further, as a polyfunctional aziridine compound, at least one selected from polyesters and polycarbonates having two or more functional groups capable of reacting with aziridinyl groups is reacted with an aziridine compound having two or more aziridinyl groups. Polymers may also be used.

Polyfunctional hydrazine-based compounds can be used as examples of hydrazine compounds. Specifically, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, etc. with about 2 to 16 carbon atoms ( In particular, saturated or unsaturated dicarboxylic acid dihydrazides having about 3 to 10 carbon atoms can be mentioned.

Examples of carbodiimide compounds include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-[3-(dimethylamino)propyl]- N'-ethylcarbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'-(2-morpholino carbodiimide compounds such as ethyl)carbodiimide meso-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, N,N'-di-p-tolylcarbodiimide; A carbodiimide compound obtained by a condensation reaction; a carbodiimide compound obtained from a polyisocyanate and a polyalkylene oxide, etc. can be used. These carbodiimide compounds may be used alone or in combination of two or more. Examples of the preferred carbodiimide cross-linking agents include "Carbodilite V-02", "Carbodilite V-02-L2", "Carbodilite SV-02", "Carbodilite V-10" and "Carbodilite SW-12G" manufactured by Nisshinbo Chemical Co., Ltd. ", "Carbodilite E-02", "Carbodilite E-03A", "Carbodilite E-05", etc. can be obtained as commercial products.

The content of the cross-linking agent in the water-based printing ink composition of the present invention may be 0; It is preferably 1 equivalent or less, more preferably 0.7 equivalent. When 0.1 equivalent or more of the cross-linking agent is contained, the water-based binder resin contained in the water-based printing ink composition can be effectively cross-linked, and it is easy to impart sufficient blocking resistance to the printing layer.

[1-7. Other ingredients]
The water-based printing ink composition of the present invention contains various additives such as leveling agents, waxes, antifoaming agents, viscosity modifiers, antistatic agents, etc., depending on the required ink performance and within a range that does not impair the effects of the present invention. may contain.

[1-8. Method for producing water-based printing ink composition]
The water-based printing ink composition of the present invention is prepared by mixing and kneading a water-based binder resin, an acyl taurinate and/or an acyl amino acid salt, an aqueous medium and, if necessary, other components, and further adding other components such as a cross-linking agent. It can be manufactured by adding and mixing components. When the water-based printing ink composition of the present invention contains a pigment, the pigment, a water-soluble acrylic resin which is a part of the water-based binder resin, a pigment dispersant, a part of the water-based medium, etc. are mixed to form a pigment dispersion. is prepared, and the remainder of the aqueous binder resin, acyl taurinate and/or acyl amino acid salt, other components, etc. are added and mixed to produce an aqueous printing ink composition.

[2. Surface printing film]
The surface printing film of the present invention comprises at least a base film A and a first printed layer B printed on at least one side of the base film A, as shown, for example, in FIG. , and a second printed layer C printed on the opposite side of the base film A on which the printed layer B is formed (the printed film X in FIG. 1 may have a second printed layer C, but not particularly limited). The ink composition, thickness, etc. of the printed layer B and the printed layer C may be the same or different.

The surface printing film of the present invention can be used, for example, as a packaging material for various products. In the case of double-sided printing, the printed layer B is arranged on the outer surface of the printed film, and the printed layer C is arranged on the inner surface thereof.

The base film A is usually a plastic film; it can be a polyolefin film such as polyethylene or polypropylene, a polyester film such as polyethylene terephthalate, polylactic acid or polycaprolactone, or various printing resin films such as nylon or vinylon. The surface of the base film A on which the printed layer B and/or printed layer C is formed is preferably subjected to surface treatment such as corona discharge treatment.

The printed layer B formed on the substrate film A in the case of single-sided printing, and the printed layer B formed on the substrate film in the case of double-sided printing are described in [1. On the other hand, the printing layer C in the case of double-sided printing is printed with the aqueous printing ink composition described in [1. Water-based printing ink composition for surface printing film]. It may be formed by printing with another ink composition. That is, on one side or both sides of the base film, the above-mentioned water-based printing ink composition is applied by a conventionally known general-purpose printing method such as gravure printing, flexographic printing, letterpress rotary printing, silk screen printing, offset printing, bar coater, comma It can be applied and printed by a coating method using a conventionally known general-purpose coater such as a coater and a spray coater. The thickness of the printed layer B and printed layer C is preferably 0.5 to 10 μm.

As shown in FIG. 1, the printed film X wound into a roll has a printed layer B and a base film A surface (when there is no printed layer C in single-sided printing), or a printed layer B and a printed layer C ( In the case of double-sided printing), the printed film printed on one side or both sides with the water-based printing ink composition of the present invention has a high anti-blocking property of the printed layer, so the effect of blocking is unlikely to occur. demonstrate.

The surface printing film of the present invention can also be, for example, a shrink film. When a shrink film is used, a heat-shrinkable film may be used as the base film. The shrink film may be a single-sided printed film or a single-sided printed film.

Moreover, the surface printing film of the present invention can also be a tubular packaging film Y as shown in FIG. The printed layer B' is formed on the outer surface of the base film A' of the tubular packaging film Y. When the tubular packaging film is wound into a roll, the printed layers B' are held in contact with each other. will be Here, since the printing layer B' is formed by printing the aqueous printing ink composition described in [1. Water-based printing ink composition for surface printing film] above, blocking between the printing layers B' is suppressed. has the effect of As described above, even in the case of single-sided printing, the surface printing film of the present invention may exhibit the effect of suppressing blocking between printed layers.

Moreover, the surface printing film of the present invention can be used as a packaging film. When used as a packaging film, a printed layer formed by printing the ink composition of the present invention is formed on the outer surface of the packaging film or on both the outer and inner surfaces of the packaging film. can be protected against

The present invention will be described below with reference to examples, but the present invention should not be construed as being limited by the description of these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".

A. The materials used in each example and comparative example are shown below.
<Pigment> Pigment Blue 15:4
<Water-soluble acrylic resin> Methacrylic acid/methyl methacrylate/stearyl methacrylate = 15/75/10, ammonia neutralized product, acid value 98 mgKOH/g, mass average molecular weight 11100, solid content 28% by mass

<Aqueous resin emulsion>
・Styrene acrylic resin emulsion: acid value 62 mgKOH/g, Tg = 7°C, solid content 36% by mass
・Acrylic resin emulsion: acid value 42 mgKOH/g, Tg = -24°C, solid content 36% by mass
・Styrene acrylic resin emulsion: acid value 87 mgKOH/g, Tg = 117°C, solid content 36% by mass
・Acrylic urethane resin emulsion: acid value 6 mgKOH/g (WEM-200U (Taisei Fine Chemical Co., Ltd.)), solid content 38% by mass
・ Urethane resin emulsion: Tg = -20 ° C. (Takelac W-6110 (Mitsui Chemicals)) solid content 32% by mass

<Acyl taurinate and/or acyl amino acid salt>
・Sodium lauroyl methyl taurate (Nikkor LMT, Nikko Chemicals)
・Sodium myristoyl methyl taurate (Nikkor MMT, Nikko Chemicals)
・Sodium palmitoyl methyl taurate (Nikkor PMT, Nikko Chemicals)
・Sodium stearoyl methyl taurate (Nikkor SMT, Nikko Chemicals)
・Sodium stearoyl glutamate (Amisoft HS-11P, Ajinomoto Co.)

<Phosphate ester surfactant> Polyoxyethylene styrenated phenyl ether phosphate (Plysurf AL, Daiichi Kogyo Seiyaku Co., Ltd.)
<Leveling agent> Surfynol 104E, Nissin Chemical Industry Co., Ltd., solid content 50% by mass
<Antifoaming agent> TEGO Foamex 825, EVONIK, solid content 20% by mass
<Wax> Chemipearl W-400, Mitsui Chemicals, solid content 40% by mass
<Crosslinking agent>
・ Epoxy curing agent (Denacol 614B, Nagase ChemteX Corporation) solid content 100% by mass
・ Aziridine-based curing agent (SU-125F, Meisei Chemical Industry Co., Ltd.) solid content 20% by mass
<Viscosity modifier> SN Thickener 601, San Nopco) Solid content 40% by mass

B. Preparation of Indigo Pigment Dispersion 45 parts by weight of Pigment Blue 15:4, 11 parts by weight of the above water-soluble acrylic resin, 2 parts by weight of pigment dispersant (Solsperse 27000), 2 parts by weight of isobutanol, water A mixture of 40 parts by mass was kneaded in a bead mill to obtain a blue pigment dispersion.

C. Preparation of water-based printing ink composition According to the formulations shown in Tables 1 and 2, the pigment dispersion prepared in B. above and each material were stirred and mixed to obtain a water-based printing ink composition. The formulations shown in Tables 1 and 2 show the mass ratio of each component including the solvent and the like. of the styrene acrylic resin (such as Example 1) contains 12.6 parts by weight of solids. In addition, in Tables 1 and 2, the mass ratio (% by mass) described for each component indicates the solid content ratio of each component.

D. Production of Printed Matter (Printed Film) A substrate film was prepared by subjecting the surface of a milky white low-density polyethylene film (thickness of 55 μm) to corona discharge treatment. Each of the water-based printing ink compositions obtained in the respective Examples and Comparative Examples was applied to the corona discharge-treated surface (single-sided printing film) of one side of the substrate film using a hand proofer to a coating amount of about 5.5. Each printed matter was obtained by coating to 0 g/m ² and drying.

E. Evaluation of printed matter The resulting printed matter was evaluated for adhesion to the substrate, blocking resistance (blocking resistance to the corona discharge-treated surface of the substrate film, blocking resistance to the untreated substrate film, or printing of the printed matter). Blocking resistance between surfaces), water resistance to rubbing, and heat resistance were evaluated. A specific evaluation method is shown below.

E-1. Evaluation of Substrate Adhesion Cellophane tape (registered trademark) was attached to the printed surface of the printed matter, and the substrate adhesion was evaluated from the degree to which the printed layer peeled off from the film when the tape was quickly peeled off. .
(Evaluation criteria)
Evaluation A: The printed layer was not peeled off from the film at all Evaluation B: Less than 15% of the area ratio of the printed layer was peeled off from the film, but it was practically acceptable.
Evaluation C: 15% or more and less than 50% of the area ratio of the printed layer was peeled from the film Evaluation D: 50% or more of the area ratio of the printed layer was peeled from the film

E-2. Evaluation of blocking resistance "Printed surface of printed material" and "Corona discharge treated surface or untreated surface of base film, or printed surface of another printed material (However, the printed surface of the two printed materials is the same ink. The printed matter and the substrate film, or the printed matter and the printed matter are superimposed with each other, and the printed matter and the printed matter are placed on top of each other, and the printed matter is placed on top of each other and dried at 40° C. for 1 hour under a load of 29.4×10 ⁴ Pa (2 kg/cm ² ). Left for days. Thereafter, the base film or the printed matter was peeled off from the printed matter by hand, and the strength of the peel resistance at that time and the degree of peeling of the printed surface of the printed layer were evaluated to evaluate the blocking resistance. "Blocking resistance (corona discharge-treated surface)" in Tables 1 and 2 is obtained when the printed surface of the printed matter is opposed to the corona discharge-treated surface of the base film; When the printed surface of the printed matter faces the printed surface of the printed matter; "Blocking resistance (untreated surface)" is the evaluation result when the printed surface of the printed matter faces the untreated surface of the base film. be.
(Evaluation criteria)
Evaluation A: There was no peeling of the printed layer, and no peeling resistance was felt.
Evaluation B: There was no peeling of the printed layer, but peeling resistance was felt.
Evaluation C: The printed layer was slightly peeled, and peeling resistance was felt strongly.
Evaluation D: Most of the printed layer was peeled off, and peeling resistance was felt strongly.

E-3. Water resistance and abrasion resistance On the printed surface of the printed matter, Kanakin immersed in water was used as the friction element, and it was reciprocated 100 times with a load of 200 g using a Gakushin tester (Daiei Kagaku Seiki Seisakusho), and the printed layer fell off. Water resistance and abrasion resistance were evaluated from the degree.
(Evaluation criteria)
Evaluation A: Evaluation that the printed layer did not come off Evaluation B: Evaluation that the printed layer came off in the range of less than 20% C: Evaluation that the printed layer came off in the range of 20% or more and less than 50% D: The printed layer was 50% or more dropped out in the range of

E-4. Evaluation of heat resistance Using a heat seal tester equipped with a hot plate having a thermal gradient of 80 to 250°C on the printed surface of the printed matter, the printed surface and aluminum foil were pressed at a pressure of 2.0 kg/cm2. , pressed for 1 second. The heat resistance was evaluated from the minimum temperature at which the ink on the printed surface transferred to the aluminum foil.
(Evaluation criteria)
Evaluation A: 200°C or higher Evaluation B: 160°C or higher and lower than 200°C Evaluation C: 140°C or higher and lower than 160°C Evaluation D: Lower than 140°C

The water-based printing ink composition of Comparative Example 1 containing no acyl taurinate and acyl amino acid salt, and Comparative Example 2 containing 0.1% by mass and 0.2% by mass of acyl taurinate and acyl amino acid salt The water-based printing ink compositions of 3 and 3 were evaluated poorly in terms of anti-blocking property against the corona discharge-treated base film surface and anti-blocking property between the printed surfaces of the printed matter. On the other hand, the water-based printing ink composition of each example containing 0.3 to 10% by mass of an acyl taurinate and an acyl amino acid salt gave good evaluations including evaluation of blocking resistance. It can be seen that the printing layer of the water-based printing ink composition containing a certain amount or more of taurinate and acylamino acid salt has excellent blocking resistance.

The water-based printing ink composition of Comparative Example 4, in which the acyl taurinate and acyl amino acid salt contents were 12.5% by mass, was not evaluated as good in terms of water resistance and abrasion resistance. On the other hand, the water-based printing ink composition of each example containing 0.3 to 10% by mass of an acyl taurinate and an acyl amino acid salt gave good evaluations including evaluation of blocking resistance. It can be seen that the printed layer of the water-based printing ink composition containing taurinate and acylamino acid salt in a certain amount or less has excellent water resistance and abrasion resistance.

In each example, good results were obtained in all evaluation items. In particular, among Examples 1-3 and 7, sodium palmitoyl methyl taurate, stearoyl methyl taurate was preferred over the aqueous printing ink compositions of Examples 1 and 2 containing sodium lauroyl methyl taurate, sodium myristoyl methyl taurate. The aqueous printing ink compositions of Examples 3 and 7 containing sodium gave better blocking resistance evaluations. From this, it can be seen that the printing layer of the water-based printing ink composition containing an acyl taurinate having moderate hydrophobicity and having an acyl group having a certain number of carbon atoms or more has excellent blocking resistance.

Among the aqueous printing ink compositions of Examples 4 to 9 containing sodium stearoyl methyl taurate, the aqueous printing inks of Examples 4 and 5 having a sodium stearoyl methyl taurate content of 0.3 and 0.5% by mass The composition resulted in slightly inferior blocking resistance with the corona discharge-treated substrate film and blocking resistance between the printed surfaces of the printed matter. On the other hand, the water-based printing ink composition of Example 9, in which the content of sodium stearoyl methyl taurate was 10.0% by mass, resulted in slightly inferior evaluation of water resistance and abrasion resistance. From this, when the content of the acyl taurinate is above a certain level, a printing layer having sufficient blocking resistance can be formed. It can be seen that a printed layer having properties can be formed.

Comparing the water-based printing ink composition of Example 7 containing wax with the water-based printing ink composition of Example 10 not containing wax, it was found that Example 7 had better evaluation of water resistance and abrasion resistance. Understand. From this, it can be seen that the printed layer of the water-based printing ink composition containing wax is excellent in water resistance and abrasion resistance.

Among Examples 10 to 12, the water-based printing ink compositions of Examples 11 and 12 containing a cross-linking agent are more resistant to water and rubbing than the water-based printing ink composition of Example 10 containing no cross-linking agent. It can be seen that the evaluation is better. From this, it can be seen that the printed layer of the water-based printing ink composition containing the cross-linking agent is excellent in water resistance and abrasion resistance.

Comparing Example 7 containing sodium stearoyl methyl taurate with Example 13 containing sodium stearoyl glutamate, it is found that Example 7 has a better evaluation of water and abrasion resistance. The reason for this is not particularly limited; sodium stearoyl methyl taurate has one anionic functional group, whereas sodium stearoyl glutamate has two anionic functional groups, and sodium stearoyl methyl taurate has hydrophobicity. Since it has a high content, it is presumed that the elution into water was suppressed, and the evaluation of water resistance and abrasion resistance was good. Thus, it can be seen that it is preferable to incorporate acyl taurate and/or acyl amino acid salt having appropriate hydrophobicity and hydrophilicity.

Among Examples 7 and 14 to 17, the water-based printing ink composition of Example 16 was slightly inferior in evaluation of water resistance and abrasion resistance. The acid value of the aqueous resin emulsion contained in the aqueous printing ink composition of Example 16 is 6 mgKOH/g, which is lower than the acid value of the aqueous resin emulsion contained in the aqueous printing ink compositions of Examples 7, 14 and 15. . Therefore, it is presumed that a water-based printing ink composition containing a water-based resin emulsion having a certain acid value or higher provides a printed layer having excellent water resistance and abrasion resistance.

Example 18 is an aqueous printing ink composition containing no pigment dispersion and is an aqueous clear ink composition or an aqueous varnish composition. It can be seen that the effect of the present invention can be obtained regardless of the presence or absence of the pigment.

Comparing the water-based printing ink composition of Example 7 containing a phosphate ester-based surfactant with the water-based printing ink composition of Example 19 not containing a phosphate ester-based surfactant, Example 7 has a better evaluation of heat resistance. I understand. From this, it can be seen that the printed layer of the water-based printing ink composition containing the phosphate surfactant is excellent in heat resistance.

The water-based printing ink composition for a surface printing film of the present invention can form a printed layer having high blocking resistance and good heat resistance and water and abrasion resistance when printed on a film. . Therefore, it is suitable as an ink composition for surface printing on a film, and can be particularly useful when high blocking resistance is required, such as when a printed film is wound up and stored.

X: Surface printing film wound up in a roll
Y: Cylindrical surface printing film wound in a roll
A, A': Base film
B, B': 1st printed layer
C: Second printed layer

Claims (5)

An aqueous printing ink composition for a surface printing film containing an aqueous binder resin and an aqueous medium,
Furthermore, the ink composition contains 0.3 to 10.0% by mass of an acyl taurinate (formula I) and/or an acyl amino acid salt (formula II) having an acyl group having 10 to 20 carbon atoms. A water-based printing ink composition for printed films.

(In formula I,
R1 represents an alkyl group, alkenyl group, alkynyl group or aromatic hydrocarbon group having 9 to 19 carbon atoms;
R2 represents a hydrogen atom or a lower alkyl group;
M indicates a counter ion for sulfonic acid. )

(In Formula II,
R3 represents an alkyl group having 9 to 19 carbon atoms, an alkenyl group, an alkynyl group, or an aromatic hydrocarbon group;
R4 represents a hydrogen atom or a lower alkyl group;
R5 represents a hydrogen atom or a lower alkyl group, and the lower alkyl group may have a hydroxyl group, a carboxyl group or a sulfhydryl group;
M indicates a counter ion for carboxylic acid. ) 2. The water-based printing ink composition for surface printing film according to claim 1, wherein the acyl taurinate and/or acyl amino acid salt is contained in the ink composition in an amount of 0.5 to 10.0% by mass. 3. The water-based printing ink composition for surface printing films according to claim 1, further comprising a phosphate surfactant. 3. The water-based printing ink composition for a surface printing film according to claim 1, wherein the water-based binder resin is at least one selected from water-based acrylic resin emulsions, water-based urethane-based resin emulsions, and water-based acrylic urethane-based resin emulsions. thing. 3. The water-based printing ink composition for surface printing film according to claim 1, further comprising a cross-linking agent.

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