JPH0680930A - Water-base printing ink composition - Google Patents

Abstract

PURPOSE:To obtain a water-base printing ink which can adhere to both a polar film and a nonpolar film and is excellent in blocking and water resistances by using a modified urethane resin obtained by polymerizing at least one specified radical-polymerizable monomer in the presence of a specified water-soluble or dispersible urethane resin as a vehicle. CONSTITUTION:The composition contains, as a vehicle component, a modified urethane resin obtained by polymerizing at least one radical-polymerizable monomer of a calculated glass transition point of 40 deg.C or above in the presence of a water-soluble or dispersible urethane resin having a total content of urethane and urea bonds of 17% or above. Examples of the above monomer include acrylic esters, methacrylic esters, hydroxylated vinyl monomers, styrene, polyalkylene oxide-containing vinyl monomers and unsaturated carboxylic acids.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aqueous printing ink composition, and more particularly to an aqueous printing ink composition having excellent adhesion to various plastic films and suitable for gravure and flexographic printing.

[0002]

2. Description of the Related Art Conventionally, solvent-based printing inks have been often used as printing inks, but in recent years, water-based printing inks have been increasingly used in view of air pollution and resource saving. However, the water-based printing ink has a drawback that it adheres to nylon and PET having a high polarity but is difficult to adhere to a polyolefin having a low polarity. Some water-based inks containing an acrylic resin or an alkyd resin as a vehicle component have been proposed in order to improve the adhesion to the polyolefin. However, many of these have insufficient adhesion to polyester films,
The reality is that there is no one type of vehicle that adheres from polar films to non-polar films.

Therefore, an object of the present invention is to provide a water-based printing ink which is excellent in blocking resistance, water resistance and the like while adhering to all polar films from non-polar films.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a modification obtained by polymerizing one or more specific radically polymerizable monomers in the presence of a specific aqueous urethane resin. The inventors have found that by using a urethane resin as a vehicle component, it is possible to obtain a water-based printing ink which is excellent in blocking resistance and water resistance while adhering to all nonpolar films from polar films. That is, the present invention is obtained by polymerizing one or more radically polymerizable monomers having a calculated glass transition point of 40 ° C. or higher in the presence of an aqueous urethane resin in which the sum of urethane and urea bonds in the urethane resin is 17% or less. A water-based printing ink composition comprising a modified urethane resin as a vehicle component.

The water-based urethane resin used in the present invention has the sum of urethane and urea bonds in the urethane resin.
17% or less, preferably 13% or less, 10
% Or less is particularly preferable. The sum of urethane and urea bonds in the urethane resin referred to here is 17% or less means that the urethane bond (-NHCOO-) occupies in the molecular weight of the urethane resin.
And the sum of the molecular weight of urea bond (-NHCONH-) is 17% or less. If this value exceeds 17%, the adhesiveness with polyolefin having low polarity is deteriorated, which is not preferable.

The aqueous urethane resin used in the present invention is
For example, it is manufactured as follows. First, an organic diisocyanate is reacted with a polyol to obtain an NCO-terminated prepolymer. The reaction is carried out using a solvent inert to isocyanates such as acetone, methyl ethyl ketone, dioxane, dimethylformamide and tetrahydrofuran. Next, an excessive amount of polyalkylene polyamine or the like is used as a chain extender in the obtained prepolymer to produce polyurethane urea polyamine. The product is reacted with a cyclic dicarboxylic acid anhydride, further neutralized with a basic substance, and the solvent is removed by distillation under reduced pressure to obtain an aqueous urethane resin. As a polyol, a diol having a carboxylic acid group is used as a prepolymer, and after chain extension with a chain extender, the carboxylic acid group of the polyol portion is neutralized with a basic substance and the solvent is removed by vacuum distillation to obtain an aqueous urethane resin. good.

Examples of the organic diisocyanate used in the production of the above-mentioned aqueous urethane resin include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethylmethane diisocyanate and 1,3-phenylene diisocyanate. , 1,6-hexamethylene diisocyanate, isophorone diisocyanate,
Aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate and alicyclic diisocyanates such as cyclohexane diisocyanate may be mentioned.

Polyols used in the production of the above water-based urethane resin include polyether polyols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, and dicarboxylic acids such as adipic acid and phthalic acid.
Examples thereof include polyester polyols which are a reaction product of 1,6-hexanediol, neopentyl glycol, and the above-mentioned polyether diols, and polycaprolactone polyol. Further, as the diol having a carboxylic acid group, 2,2-dimethylolpropionic acid, 2,2
Examples include dimethylol butyric acid and 2,2-dimethylol valeric acid.

Examples of the chain extender used in the production of the above-mentioned aqueous urethane resin include polyalkylene polyamines such as diethylene triamine, triethylene tetramine and tetraethylene pentamine, polyols such as ethylene glycol and propylene glycol, ethylene diamine, propylene diamine and hexa. Aliphatic such as methylenediamine, diphenyldiamine, piperazine, isophoronediamine,
Examples thereof include alicyclic and aromatic diamines.

As the cyclic dicarboxylic acid anhydride used in the production of the above aqueous urethane resin, maleic anhydride,
Examples thereof include succinic anhydride, phthalic anhydride, trimellitic anhydride, and itaconic anhydride.

Examples of the basic substance used as a neutralizing agent in the production of the aqueous urethane resin include trimethylamine, triethylamine, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide and the like.

The aqueous urethane resin thus obtained was added with a radical polymerization initiator and a calculated glass transition point of 40 ° C.
Add one or more radically polymerizable monomers as described above,
The modified urethane resin used in the present invention can be obtained by polymerizing by a usual method. Acrylic acid ester (methyl, ethyl,
Acrylic esters such as propyl, butyl, 2-ethylhexyl and lauryl), methacrylic esters (methyl, ethyl, propyl, butyl, 2-ethylhexyl,
Methacrylic acid esters such as lauryl), hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, aromatic unsaturated hydrocarbons such as styrene and α-methylstyrene, polyethylene glycol acrylate, polyethylene glycol methacrylate and methoxy. Polyalkylene oxide group-containing vinyl monomers such as polyethylene glycol acrylate and methoxy polyethylene glycol methacrylate,
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like can be mentioned, and those having a calculated glass transition point (Tg) of 40 ° C. or higher in these combinations are preferable, and 60 ° C.
The above is more preferable. If the calculated Tg is less than 40 ° C, the blocking resistance is inferior, which is not preferable. The calculation Tg referred to here is the one calculated from the following calculation formula.

[0013]

[Equation 1]

(In the formula, W ₁ and W ₂ are monomer 1 and monomer 2
In the polymer, Tg ₁ and Tg ₂ are polymer 1,
The Tg of the homopolymer of polymer 2 is shown. As the radical polymerization initiator used in the production of the modified urethane resin, not only a water-soluble initiator used in ordinary emulsion polymerization but also an oil-soluble initiator can be used. Examples include ammonium persulfate, potassium persulfate, azobiscyanovaleric acid, azobisisobutyronitrile, t-butyl hydroperoxide and the like. A redox catalyst composed of a combination of these radical generators with sulfites and sulfoxylates can also be used.

The content of the modified urethane resin thus obtained in the aqueous printing ink composition of the present invention is 5 to 50% by weight, preferably 10 to 40% by weight in terms of solid content. The water-based printing ink composition of the present invention may optionally contain a water-soluble resin such as styrene / maleic acid resin, a pigment, a wax, a defoaming agent, a plasticizer, a film-forming aid, etc. within a range that does not impair the performance thereof. It can be added.

[0016]

The water-based printing ink composition of the present invention exhibits good adhesion to all plastic films such as polyester and polyolefin as well as plain paper by gravure printing or flexographic printing, and further,
It also has blocking resistance and water resistance.

[0017]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The parts and% used in Examples and Comparative Examples are
Unless stated otherwise, the unit represents parts by weight and% by weight.

Synthesis Example 1 Production of Aqueous Urethane Resin I Adipic Acid / Neopentyl Glycol / Molecular Weight 2000
1,6-hexanediol type polyester diol 200
Parts, molecular weight 350 bisphenol A / polyethylene glycol type polyether diol 8.75 parts, isophorone diisocyanate 46.9 parts, di-n-butyltin dilaurate
0.05 parts and 109.6 parts of methyl ethyl ketone were reacted at 80 ° C. for 3 hours to obtain a urethane prepolymer. Next, 365.3 parts of methyl ethyl ketone and 11.5 parts of diethylene triamine were dissolved, and the above prepolymer was added dropwise at 50 ° C. over 1 hour to obtain a polyurethane urea polyamine. Next, after adding 16.5 parts of succinic anhydride and reacting at 50 ° C for 1 hour, 11.2 parts of 25% ammonia water and 660 parts of ion-exchanged water were added and methyl ethyl ketone was distilled off to obtain an aqueous urethane resin having a concentration of 30%. It was This is called aqueous urethane resin I. The sum of urethane bonds and urea bonds in this aqueous urethane resin I is about 9%.

Synthetic Example 2 Production of Aqueous Urethane Resin II Adipic Acid / Neopentyl Glycol / Molecular Weight 2000
1,6-hexanediol type polyester diol 200
Parts, molecular weight 350 bisphenol A / polyethylene glycol-based polyether diol 51.6 parts, isophorone diisocyanate 79.1 parts, di-n-butyltin dilaurate
0.05 parts and 141.7 parts of methyl ethyl ketone were reacted at 80 ° C. for 3 hours to obtain a urethane prepolymer. Next, 472.4 parts of methyl ethyl ketone and 14.6 parts of diethylenetriamine were dissolved, and the above prepolymer was added dropwise at 50 ° C. over 1 hour to obtain a polyurethane urea polyamine. Next, after adding 21.0 parts of succinic anhydride and reacting at 50 ° C. for 1 hour, 14.2 parts of 25% ammonia water and 855 parts of ion-exchanged water were added to distill off methyl ethyl ketone to obtain an aqueous urethane resin having a concentration of 30%. It was This is called aqueous urethane resin II. The sum of urethane bonds and urea bonds in this aqueous urethane resin II is about 12%.

Synthesis Example 3 Preparation of aqueous urethane resin III 100 parts of adipic acid / polyethylene glycol type polyester diol having a molecular weight of 1000, 70 parts of bisphenol A / polyethylene glycol type polyether diol having a molecular weight of 350, isophorone diisocyanate 144 parts, methyl ethyl ketone 135 Parts were reacted at 80 ° C. for 5 hours to obtain a urethane prepolymer. Then, methyl ethyl ketone 4
While dissolving 49.3 parts and 45.2 parts of diethylenetriamine,
The above prepolymer was added dropwise at 50 ° C. over 1 hour to obtain a polyurethaneurea polyamine. Next, succinic anhydride
After adding 61.8 parts and reacting at 50 ° C. for 1 hour, 42 parts of 25% ammonia water and 980 parts of ion-exchanged water were added to distill off methyl ethyl ketone to obtain an aqueous polyurethane resin having a concentration of 30%. This is called aqueous urethane resin III. The sum of urethane bond and urea bond in this water-based urethane resin III is about
21%.

Example 1 A reaction vessel equipped with a reflux condenser, a thermometer and a stirrer was charged with a composition having the following composition and allowed to stand for 1 hour while being replaced with N ₂ gas. Aqueous urethane resin I 100 parts Styrene 15 Potassium persulfate 0.075 Ion-exchanged water 13.6 Then, the internal temperature was left at 80 ° C. and reaction was carried out for 5 hours to obtain a modified urethane resin emulsion. The resulting emulsion was stable at 35% solids. Next, the above modified urethane resin emulsion was used to blend with the following composition, and the mixture was dispersed in a sand mill for 5 hours to obtain an ink.

-Inking- The above-mentioned modified urethane resin emulsion 60.0 parts Lionol Blue KLH (manufactured by Toyo Ink Co., Ltd.) 12.5 Isopropyl alcohol 1.0 Ion-exchanged water 26.5 Examples 2-6, Comparative Examples 1-5 Water-based urethane resin and radical-polymerizable monomer Various urethane resin emulsions were prepared in the same manner as in Example 1 except that the kind and amount of were changed to the formulation shown in Table 1, and these urethane resin emulsions were used to form an ink with the same composition as in Example 1.

[0023]

[Table 1]

Test Example The inks prepared in Examples 1 to 6 and Comparative Examples 1 to 5 were applied to an OPP film (Toyobo Peyron P using a bar coater (No 04)).
2161) and PET film (Toyobo Ester E5400) were printed, and the physical properties were evaluated by the following methods. The results are shown in Table 2.

<Evaluation Method> Adhesiveness: Peeling was performed using cellophane tape manufactured by Nichiban, and the following criteria were evaluated. ◎ Not peeled ○ Slightly peeled × Remarkably peeled Blocking resistance: The degree of peeling of the ink surface after standing for 20 hours under a pressure of 40 ° C and 1 kg / cm ² was evaluated according to the following criteria. ◎ Not peeled ○ Slightly peeled × Remarkably peeled Water resistance: Rubbing the ink surface with gauze moistened with water, the degree of rubbing until the ink surface was peeled off was evaluated, and evaluated according to the following criteria. ◎ No peeling 20 times or more ○ Peeling 10 to 20 times △ Peeling 5 to 10 times × Peeling 5 times or less

[0026]

[Table 2]

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[Procedure amendment]

[Submission date] October 12, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

Examples of the organic diisocyanate used for producing the water-based urethane resin include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate and xylylene diisocyanate.
Anates, aromatic diisocyanates such as 1,3-phenylene diisocyanate, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,4-tetramethylene diisocyanate, isophorone diisocyanate
DOO, cycloaliphatic diisocyanates such as cyclohexylene diisocyanate.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

Polyols used in the production of the above water-based urethane resin include polyether polyols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, and dicarboxylic acids such as adipic acid and phthalic acid.
Examples thereof include 1,6-hexanediol, neopentyl glycol, polyester polyols which are a reaction product with the above polyether polyol, and polycaprolactone polyol. Further, as the diol having a carboxylic acid group, 2,2-dimethylolpropionic acid, 2,2
Examples include dimethylol butyric acid and 2,2-dimethylol valeric acid.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

Synthesis Example 1 Production of Aqueous Urethane Resin I Adipic Acid / Neopentyl Glycol / Molecular Weight 2000
1,6-hexanediol type polyester diol 200
Parts, bisphenol A / polypropylene grayed <br/> polyether diol 8.75 parts of recall based molecular weight of 350, 46.9 parts of isophorone diisocyanate, 0.05 parts of dilaurate n- butyltin allowed to react for 3 hours methyl ethyl ketone 109.6 parts at 80 ° C. To obtain a urethane prepolymer. Then 365.3 parts of methyl ethyl ketone, 11.5 of diethylenetriamine
While dissolving parts, the above prepolymer was added dropwise at 50 ° C. over 1 hour to obtain a polyurethaneurea polyamine.
Next, after adding 16.5 parts of succinic anhydride and reacting at 50 ° C for 1 hour, 11.2 parts of 25% ammonia water and 660 parts of ion-exchanged water were added and methyl ethyl ketone was distilled off to obtain an aqueous urethane resin having a concentration of 30%. It was This is called aqueous urethane resin I.
The sum of urethane bonds and urea bonds in this aqueous urethane resin I is about 9%.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

Synthetic Example 2 Production of Aqueous Urethane Resin II Adipic Acid / Neopentyl Glycol / Molecular Weight 2000
1,6-hexanediol type polyester diol 200
Department, polyether diol 51.6 parts of bisphenol A / polypropylene grayed <br/> recall system with a molecular weight of 350, 79.1 parts of isophorone diisocyanate, 0.05 parts of dilaurate n- butyltin allowed to react for 3 hours methyl ethyl ketone 141.7 parts at 80 ° C. To obtain a urethane prepolymer. Then, methyl ethyl ketone 472.4 parts, diethylenetriamine 14.6
While dissolving parts, the above prepolymer was added dropwise at 50 ° C. over 1 hour to obtain a polyurethaneurea polyamine.
Next, after adding 21.0 parts of succinic anhydride and reacting at 50 ° C. for 1 hour, 14.2 parts of 25% ammonia water and 855 parts of ion-exchanged water were added to distill off methyl ethyl ketone to obtain an aqueous urethane resin having a concentration of 30%. It was This is called aqueous urethane resin II.
The sum of urethane bonds and urea bonds in this aqueous urethane resin II is about 12%.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

[0020] 100 parts of a polyester diol of Synthesis Example 3 aqueous urethane resin III adipate / polyethylene glycol of having molecular weight 1,000, 70 parts of polyether diol of bisphenol A / polypropylene glycol of molecular weight 350, 144 parts of isophorone diisocyanate, methyl ethyl ketone A urethane prepolymer was obtained by reacting 135 parts at 80 ° C. for 5 hours. Then, methyl ethyl ketone
The above-mentioned prepolymer was added dropwise at a temperature of 50 ° C. over 1 hour to a solution of 449.3 parts and 45.2 parts of diethylenetriamine to obtain a polyurethaneurea polyamine. Next, after adding 61.8 parts of succinic anhydride and reacting at 50 ° C for 1 hour, 42 parts of 25% ammonia water and 980 parts of deionized water were added to distill off methyl ethyl ketone to obtain an aqueous polyurethane resin having a concentration of 30%. It was This is called aqueous urethane resin III. The sum of urethane bonds and urea bonds in this aqueous urethane resin III is about 21%.

Claims (1)

[Claims] 1. A polymer obtained by polymerizing one or more radically polymerizable monomers having a calculated glass transition point of 40 ° C. or higher in the presence of an aqueous urethane resin having a total urethane and urea bond content of 17% or less in the urethane resin. An aqueous printing ink composition comprising a modified urethane resin as a vehicle component.