JP3471087B2 - Aqueous printing ink composition for lamination - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous polyurethane resin.
About laminate for aqueous printing ink composition using a liquid. More particularly, excellent in long-term storage stability, good adhesion to a laminate for aqueous printing ink composition using Lupo Caixaforum <br/> Tan resin aqueous solution having a lamination suitability and redissolvability.

[0002]

2. Description of the Related Art In recent years, with the diversification of packaging containers and the higher functionality of synthetic resin products such as synthetic leather, printing inks and various coating agents used for decoration or surface protection are required to have high performance. Is becoming more common.

For example, in the field of printing inks for plastic films, it is necessary to have excellent printability, adhesion to a wide variety of films, blocking resistance, gloss, and color development.

Further, when the printed matter is used as a food packaging container, a polymer layer is provided on the printing surface of the ink by a method called lamination to prevent direct contact between the content and the ink, The ink used for this laminating process should not only adhere well to the printing substrate, but also have excellent adhesiveness (lamination suitability) with the film to be laminated. I have to.

Since these ink performances mainly depend on the performance of the binder resin, among the binder resins, a polyurethane resin having excellent adhesiveness to a wide variety of films and excellent laminating suitability is used as the binder resin, and solvent properties are obtained. Laminating inks have often been used.

However, recently, from the viewpoints of environmental problems, resource saving, labor safety, food hygiene, etc., there is a strong demand for water-based printing inks.

Generally, as a method for making a solvent-based ink aqueous, a binder resin used in a solvent-based ink is dispersed in water in the presence of an emulsifier (water-dispersible type), or an acid is incorporated into a molecule. There is a method in which a group is introduced and dissolved in water (water-soluble type) or dispersed (self-emulsifying type) in the presence of a basic compound to prepare an ink using water as a medium.

Solvent-based inks containing a polyurethane resin as a binder resin are also made water-based by the above-mentioned method. Generally, when the above-mentioned water-dispersible type polyurethane resin is used, pigment dispersibility, ink fluidity and re-dissolution are obtained. Tend to be poor in sex.

Therefore, the water-soluble or self-emulsifying type polyurethane resin is used as a basic binder, and as a method for introducing an acid group into the molecule of the polyurethane resin, there are the following methods.

A method utilizing a diol monocarboxylic acid such as dimethylolpropionic acid (JP-A-4-1784)
No. 18, etc.).

A polyester diol having a constitutional unit in which two carboxyl groups are bonded to one aromatic ring in the molecule, such as an ester of pyromellitic dianhydride and trimethylolpropane or an ester of pyromellitic dianhydride and a diol compound. Method of use (Japanese Patent Laid-Open No. 5-17109)
No. 1 publication).

However, in the polyurethane resin obtained by the method (1), when the amount of the carboxyl group required to dissolve the basic compound in the aqueous solution is introduced into the molecule, the molecule itself becomes hard and the adhesiveness of the ink obtained is increased. Since there is a tendency to decrease, it becomes difficult to obtain a binder having sufficient solubility and adhesiveness.

On the other hand, in the polyurethane resin obtained by the above method, the curing of the molecule itself can be prevented, but it is hydrolyzed by the basic compound, and the adhesiveness and storage stability of the ink with time deteriorate.

[0014]

[SUMMARY OF THE INVENTION Therefore, purpose of the present invention, the by conventional solve the problems of the art, storage stability over a long term, Ba polyurethane resin aqueous solution not to lower the adhesion Indah The present invention provides a water-based printing ink composition having a suitability for laminating used as.

[0015]

Means for Solving the Problems] The present invention, organic diisocyanate component, the polymeric diol component and chain extender, and further with a reaction terminating agent are reacted optionally obtained
It is, and has a structural unit represented by the following general formula (I) and (or) (II), a number average molecular weight 2,000
200,000, a polyurethane resin having an acid value of 5 to 100
Containing a polyurethane resin aqueous solution dissolved or dispersed in water in the presence of a basic compound , and a pigment as essential components
Water-based printing ink composition for laminating characterized by
The product (the invention of claim 1).

[0016]

[Chemical 2]

(In the formula, X represents --CH _2- , --CO-- or --O--).

As a preferable embodiment of the above invention, the following aqueous printing ink set for laminating (a) and (b)
Regarding the product .

The laminating water according to claim 1, wherein the polymer diol component (a) has a structural unit represented by the general formula (I) and / or (II) in the molecule.
Sex printing ink composition (second aspect of the present invention).

(B) An amount such that the total carboxyl groups derived from the constitutional units represented by the general formulas (I) and / or (II) are 30 mol% or more of the total carboxyl groups in the polyurethane resin molecule. The content of claim 1 or 2
Aqueous printing ink composition for lamination (invention of claim 3).

[0021]

[0022]

ACTIONS AND EXAMPLES The aqueous polyurethane resin liquid of the present invention has a number average molecular weight of 2,000 to 20 having the constitutional units represented by the general formulas (I) and / or (II).
0,000, polyurethane resins having an acid value of 5 to 100 is, is characterized in that present in a dissolved or dispersed state in the presence sewage of a basic compound, it as binder <br/> over resin aqueous ink composition When used, it exhibits excellent long-term storage stability, adhesiveness, laminating suitability and re-dissolving property.

The organic diisocyanate component, polymer diol component and chain extender used in the polyurethane resin used in the present invention will be described.

First, the organic diisocyanate component is not particularly limited as long as it is an organic diisocyanate capable of forming a polyurethane resin, and specifically, for example, a fatty acid such as hexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate. Group diisocyanate compounds, isophorone diisocyanate, hydrogenated xylylene diisocyanate, alicyclic diisocyanate compounds such as 4,4′-dicyclohexylmethane diisocyanate, xylylene diisocyanate, aromatic aliphatic diisocyanate compounds such as tetramethylxylylene diisocyanate, toluylene diisocyanate, Aromatic diisocyanate compounds such as diphenylmethane diisocyanate can be mentioned. Among them,
The alicyclic or araliphatic diisocyanate compound is preferable from the viewpoint of improving the adhesiveness to various films and the re-solubility of the aqueous printing ink.

Next, the polymer diol component will be described.

First, as a polymer diol component (hereinafter, also referred to as polymer diol component (A)) containing a structural unit represented by the general formula (I) and / or the general formula (II) in the molecule, , 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride (formula (III)), 3,3', 4,4 '
-Diphenylmethanetetracarboxylic dianhydride (formula (I
V)), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (formula (V)), 4,4'-oxydiphthalic dianhydride (formula (VI)) The polyester diol obtained by reacting the tetracarboxylic dianhydride of 1 with the low molecular diol compound and / or the high molecular diol compound can be used.

[0027]

[Chemical 3]

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

The low molecular weight diol compound is 1,
3-propanediol, 1,4-butanediol, 1,
Linear glycols such as 6-hexanediol, 1,
2-propanediol, neopentyl glycol, 3-
Examples thereof include branched glycols such as methyl-1,5-pentanediol and ethylbutylpropanediol, and low molecular diol components such as ether diols such as diethylene glycol and triethylene glycol.

The high molecular weight diol compound may be obtained by polycondensation of the low molecular weight diol compound with a dibasic acid component such as adipic acid or phthalic acid, or by ring-opening reaction of a cyclic ester compound such as lactone. Polyester diols, polyether diols obtained by polymerizing or copolymerizing ethylene oxide, propylene oxide, tetrahydrofuran, etc., and a carbonate component such as alkylene carbonate, diallyl carbonate, dialkyl carbonate or phosgene, and Examples thereof include polycarbonate diols and polybutadiene glycols obtained by reacting with a molecular diol compound.

When the above-mentioned tetracarboxylic dianhydride is reacted with the low molecular weight diol compound and / or the high molecular weight diol compound, they are mixed at a predetermined ratio and then 70-
A method of heating to 140 ° C. is generally used.

Further, other usable polymer diol components (polymer diol components containing no structural unit represented by general formula (I) and / or general formula (II) in the molecule, hereinafter referred to as polymer diol) Component (B)) is obtained by reacting the above-mentioned polymer diol compound with pyromellitic dianhydride, or by ring-opening polymerization of lactones with dimethylolpropionic acid as an initiator. In addition to the above-mentioned polymer diol compound having a carboxyl group, the polymer diol compound itself can be used as the polymer diol component.

[0035] When used in the aqueous polyurethane resin solution of the present invention the binder over the printing ink composition, adhesion to the plastic film, in view of such a laminate suitability, polymeric diol component (A) And (B)
It is desirable to use polyester diols and polycarbonate diols as the high molecular diol compound, and it is preferable to use polyester diols in order to impart the suitability for boiling and retorting.

The molecular weight (number average molecular weight, the same applies hereinafter) of the above polymeric diol components (A) and (B) is preferably 500 to 10,000 from the viewpoint of optimizing the film hardness and cohesive force of the obtained polyurethane resin. And even 1
Those of 000 to 6000 can be preferably used.

Further, by using the high molecular weight diol component and the low molecular weight diol compound in combination so that the molecular weight is within the above range, it is possible to obtain a polyurethane resin which can impart good performance.

Next, the chain extender will be described.

First, the chain extender containing a structural unit represented by the general formula (I) and / or the general formula (II) in the molecule (hereinafter, also referred to as chain extender (A)) is At least one tetracarboxylic acid dianhydride selected from carboxylic acid dianhydride and the low molecular weight diol compound or the low molecular weight diamine compound are n mol: n + 1 mol (provided that n is an integer of about 1 to 3). A diol compound or a diamine compound obtained by reacting with can be used.

Here, as the low molecular weight diamine compound,
Ethylenediamine, 1,4-butanediamine, 1,6-
Aliphatic and alicyclic diamines such as hexanediamine, aminoethylethanolamine and isophoronediamine can be used.

When the tetracarboxylic dianhydride and the low molecular weight diamine are reacted with each other, they are generally mixed at a predetermined ratio and then heated to room temperature to 60 ° C.

Further, other usable chain extenders (chain extenders not containing the structural unit represented by the general formula (I) and / or general formula (II) in the molecule, hereinafter referred to as chain extender ( Also referred to as B)) are ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
Hexanediol, glycol such as diethylene glycol, hydrazine, the low molecular weight diamine compound, and the following general formula (VII):

[0043]

[Chemical 7]

(In the formula, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms),
A compound represented by, or succinic acid, adipic acid or the like and a carboxyl group-containing aliphatic polyol obtained by reacting with a lower polyol, phthalic acid, trimellitic acid, pyromellitic acid or an anhydride thereof and a lower polyol. Carboxyl group-containing aromatic polyols obtained by the reaction can be mentioned, and further, within the use range in which the polyurethane resin can be stably dispersed in water, the above-mentioned bifunctional chain extender, glycerin, 1,2,3-tri- Multifunctional chain extension of aliphatic polyols such as methylolpropane and pentaerythritol, alicyclic polyols such as 1,3,5-cyclohexanetriol, and aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Agents can be used together.

Further, in the present invention, a reaction terminator is used if necessary.

The reaction terminator is used for chain-extending the urethane prepolymer with a chain extender and then reacting with the remaining isocyanate group to eliminate the reactivity, and n-propylamine, n -Butylamine, N,
Alkylamines such as N-di-n-butylamine, alkanolamines such as monoethanolamine and diethanolamine, hydrazine, alkyldihydrazine,
Examples thereof include hydrazines such as alkyldihydrazide and monoalcohols such as methanol and ethanol.

A method for producing a polyurethane resin using the above organic diisocyanate component, polymer diol component, chain extender and reaction terminator will be described.

First, an organic diisocyanate component and a polymer diol component are mixed in a molar ratio of (1.3 to 3.0): 1, more preferably (1.5 to 2.0): 1, and then both are mixed. Depending on the reactivity, the necessity or type of use of the water-miscible solvent or catalyst, the reaction temperature, etc. are determined, and the reaction is carried out by a known method to synthesize the urethane prepolymer. Then
A chain extender and, if necessary, a solvent, a catalyst and the like are added and reacted, and a reaction terminator is further reacted to complete the production. Instead of using the reaction terminator, a method of using an excessive amount of chain extender to terminate the reaction or a method of simultaneously adding the chain extender and the reaction terminator may be used.

As the water-miscible solvent used in the production of the polyurethane resin, methyl acetate, ethyl acetate, acetone, N-methylpyrrolidone and the like can be mentioned, and as the catalyst, octyl primary Examples thereof include tin, dibutyltin diacetate, tetrabutoxy titanate, triethylamine and triethylenediamine.

The polyurethane resin obtained by the above materials and production method has a number average molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000. Number average molecular weight of polyurethane resin is 20,
When it is less than 00, the cohesive force of the resin film is poor and sufficient adhesiveness cannot be obtained, while when it exceeds 200,000,
Dispersion or dissolution stability in water decreases.

Next, a method of making the polyurethane resin aqueous will be described.

The polyurethane resin is made water-based by a method of dissolving or dispersing the polyurethane resin having a carboxyl group in the molecule in water in the presence of a basic compound.

Here, the amount of the carboxyl group introduced into the molecule is such that the carboxyl group derived from the structural units represented by the general formulas (I) and / or (II) is an essential component and the acid of the polyurethane resin is The amount is 5 to 100, preferably 20 to 60. When the acid value of the polyurethane resin is smaller than the above range, sufficient solubility or dispersibility in water cannot be obtained. On the other hand, when the acid value is larger than the above range, various coating agents using the polyurethane resin as a binder may be used. Water resistance is reduced, which is not preferable.

The above general formulas (I) and / or (II)
The total carboxyl group derived from the structural unit represented by does not cause a viscosity change or the like even when stored for a long period of time, and since the resin film has appropriate flexibility, it generally varies depending on the acid value of the polyurethane resin. Specifically, it is preferably 10 mol% or more, more preferably 20 mol% or more of all carboxyl groups in the polyurethane resin molecule.

When the aqueous polyurethane resin solution of the present invention is used as a binder for printing ink, it does not deteriorate the printability and the adhesiveness to a plastic film even if it is stored for a long period of time, and therefore it has the general formula (I). The total carboxyl groups derived from the structural units represented by and / or (II) are 30 mol% or more of the total carboxyl groups in the polyurethane resin molecule, and more preferably 50 mol% or more.

On the other hand, examples of the basic compound used to disperse or dissolve the polyurethane resin in water include ammonia, organic amines and alkali metal hydroxides. Specifically, as the organic amine, Alkylamines such as diethylamine, triethylamine and ethylenediamine, alkanolamines such as monoethanolamine, ethylethanolamine and diethylethanolamine, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Among them, those that easily volatilize at room temperature or under slight heating (for example, ammonia and alkylamine) are preferable in order to improve the drying property.

The amount of the basic compound used to dissolve or disperse the polyurethane resin in water is
0.15 of the amount necessary to neutralize the polyurethane resin
~ 1.2 equivalents are preferable, and 0.8-1.1 equivalents are more preferable. When the amount of the basic compound used is less than 0.15 equivalent, it tends to be difficult to disperse the polyurethane resin in water. On the other hand, the basic compound is 1.
Although it can be used in excess of 2 equivalents, the effect of dissolving or dispersing the polyurethane resin in water is not much different from the effect of using 1.2 equivalents.

The polyurethane resin of the present invention is preferably dissolved or dispersed in water at a solid content of 5 to 50% (weight%, the same applies hereinafter), more preferably 10 to 40%. When the solid content is less than 5%,
If the concentration is too low, the use is limited. On the other hand, if it exceeds 50%, it is difficult to disperse or dissolve in water, which is not preferable.

The polyurethane resin may be made aqueous by using a basic compound or the like after producing the polyurethane resin, or by making the urethane prepolymer aqueous and then reacting it with a chain extender or the like. You may let me.

Next, an aqueous printing ink composition using the aqueous polyurethane resin liquid of the present invention as a binder resin will be described.

The water-based printing ink composition of the present invention is a water-based printing ink composition for a plastic film or the like, which comprises the above-mentioned polyurethane resin water-based liquid and a pigment as essential components and a water-miscible solvent as an optional component. .
If necessary, water is further added to adjust the concentration.

Examples of the pigments include inorganic pigments (titanium oxide, red iron oxide, carbon black, etc.), organic pigments (azo pigments, condensed polycyclic pigments, phthalocyanine pigments, etc.), which are generally used in printing inks, paints, and the like. Pigments (calcium carbonate, barium sulfate, aluminum hydroxide, etc.) can be used.

As the aqueous binder resin, the above-specified polyurethane resin is used as an essential component, but for the purpose of improving other performance of the ink, cellulose resin, acrylic resin,
Various other water-based resins such as polyester resins, styrene-maleic acid resins, ethylene-acrylic acid resins, and polyurethanes that do not contain structural units represented by the general formulas (I) and / or (II) in the molecule. A resin or the like may be used in combination within a range that does not impair the effects of the present invention.

Further, depending on the necessity of ink performance, various water-miscible solvents such as lower alcohols such as methanol, ethanol, isopropanol and methoxypropanol or lower alkoxypropanol and antiblocking agents, defoaming agents, crosslinking agents and the like. Additives can also be included.

The above-mentioned aqueous solution of polyurethane resin is contained in the aqueous printing ink composition in an amount of 5 to 30%, more preferably 10 to 25%, in terms of solid content, from the viewpoint of imparting appropriate fluidity and ink film cohesion. Preferably.

The pigment is preferably contained in the aqueous printing ink composition in an amount of 1 to 50%, more preferably 5 to 40%, from the viewpoint of balancing the coloring power and fluidity of the ink. .

When a water-miscible solvent is used, it is preferably contained in the aqueous printing ink composition in an amount of 5 to 20%.

As a method for producing an aqueous printing ink using the above materials, first, a pigment and an aqueous binder resin such as an aqueous solution of a polyurethane resin are stirred and mixed, and then a usual dispersing device (for example, a red devil type dispersing machine is used). ) And kneading with the above components, and then adding and mixing the predetermined components.

The aqueous printing ink composition obtained from the present invention is excellent in long-term storage stability and has good adhesiveness and resolubility.

Next, a method of using the aqueous printing ink composition of the present invention will be described.

First, as the plastic film on which the aqueous printing ink composition of the present invention is printed, various plastic films such as polyolefin, modified polyolefin, polyester, nylon and polystyrene can be used. In particular, corona discharge treatment or surface coating treatment is used. A plastic film is preferred.

The aqueous printing ink composition of the present invention can be printed by a flexographic or gravure printing method using a known flexographic printing machine or gravure printing machine.

Further, the printed matter obtained by the above printing method can be laminated by extrusion laminating method and dry laminating method.

The aqueous printing ink composition obtained by the above method has good re-dissolving property, high adhesiveness even after long-term storage and suitability for lamination.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Unless otherwise specified, parts in the examples and the like represent parts by weight.

Production Example 1 A four-necked flask equipped with a stirrer, a cooling pipe, a nitrogen gas introduction pipe and a dropping funnel was used, and the molecular weight of (Poly-3-
Methyl-1,5-pentane adipate) diol (3-
(Diol obtained by polycondensation of methyl-1,5-pentanediol and adipic acid, the same applies hereinafter) 300 parts, 3,
29.4 parts of 3 ', 4,4'-diphenyltetracarboxylic dianhydride was charged and reacted at a reaction temperature of 120 to 140 ° C for 1 hour. After cooling to 50 ° C., 40 parts of isophorone diisocyanate was charged and reacted at 60 to 80 ° C. for 4 hours, and then 740 parts of water, 131 parts of isopropanol and 20.2 parts of triethylamine were charged to be water-solubilized. Furthermore, 10.8 parts of isophoronediamine and 1.6 of hydrazine
Parts, and reacted for 20 minutes to give a polyurethane resin aqueous solution No. 1 was obtained (molecular weight of polyurethane resin 23,000, acid value 28).

The acid value and the molecular weight were measured by the following methods.

(Acid value) It was determined by the neutralization titration method using 1 / 10N alcoholic potassium hydroxide.

(Molecular weight) The number average molecular weight was measured by the GPC method by a conventional method.

Production Example 2 Instead of 29.4 parts of 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic acid dianhydride 30. 8 parts, and using the same apparatus, composition and method as in Production Example 1 except that water was 743 parts, a polyurethane resin aqueous solution No. 2 (the molecular weight of polyurethane resin is 2)
3,000, acid value 28).

Production Example 3 In place of 29.4 parts of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride 32. Polyurethane resin aqueous liquid No. 3 having a solid content of 30% was prepared using the same apparatus, composition and method as in Production Example 1 except that 2 parts and 746 parts of water were used. 3 (molecular weight of polyurethane resin 23,
000, acid value 28).

Production Example 4 Instead of 29.4 parts of 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 31.0 parts of 4,4′-oxydiphthalic dianhydride and water were added. The same apparatus, composition and method as in Production Example 1 except that 743 parts were used, and a polyurethane resin aqueous solution No. 4 was obtained (molecular weight of polyurethane resin 23,000, acid value 28).

Production Example 5 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride 29.4 parts was replaced with 3,3', 4,4'-benzophenone tetracarboxylic dianhydride 9. 7 parts, pyromellitic dianhydride 15.3 parts, and using the same apparatus, composition and method as in Production Example 1 except that water was 729 parts, polyurethane resin aqueous liquid No. 3 having a solid content concentration of 30%. 5 (polyurethane resin molecular weight 22,000, acid value 2
8). In addition, in this production example, when the total carboxyl groups derived from the structural units represented by the general formulas (I) and / or (II) are 30 mol% of the total carboxyl groups in the polyurethane resin molecule. Met.

Production Example 6 300 parts of (poly-3-methyl-1,5-pentaneadipate) diol having a molecular weight of 1500 was added to 450 parts,
29.4 parts of 3 ', 4,4'-diphenyltetracarboxylic dianhydride to 58.8 parts, 740 parts of water to 1063 parts, 131 parts of isopropanol to 188 parts and 20.2 parts of triethylamine to 40. 4 except for changing the parts, manufacturing
In the same apparatus and method as concrete examples 1, a solid concentration of 30% polyurethane resin aqueous solution No. 6 was obtained (polyurethane resin molecular weight 34,000, acid value 40).

Production Example 7 The same apparatus and method as Production Example 1 were used except that 10.8 parts of isophoronediamine was changed to 12.2 parts and 1.6 parts of hydrazine was changed to 0.8 parts, and the solid content concentration was 30%. Polyurethane resin aqueous liquid No. 7 was obtained (molecular weight of polyurethane resin 67,000, acid value 40).

Production Example 8 Instead of 300 parts of (poly-3-methyl-1,5-pentaneadipate) diol having a molecular weight of 1500, a molecular weight of 5 was used.
20 of poly (neopentyl adipate) diol of 00
0 parts, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride 29.4 parts to 88.2 parts, water 740 parts to 6 parts
24 parts to 110 parts of the 131 parts of isopropanol, except for changing 20.2 parts of triethylamine in 60.6 parts of the same apparatus and manner as in Example 1, a solid concentration of 30
% Polyurethane resin aqueous liquid No. 8 was obtained (molecular weight of polyurethane resin 20,000, acid value 99).

Comparative Production Example 1 The same apparatus as in Production Example 1 was used.
Methyl-1,5-pentane adipate) diol 300
And 21.8 parts of pyromellitic dianhydride were charged and reacted at a reaction temperature of 90 to 100 ° C. for 2 hours. After cooling to 50 ° C,
Charge 40 parts of isophorone diisocyanate, 50-6
The reaction was carried out at 0 ° C. for 2 hours, and then 682 parts of water, 120 parts of isopropanol, and 20.2 parts of triethylamine were charged and water-solubilized.

Further, 10.8 parts of isophoronediamine,
1.6 parts of hydrazine was added and reacted for 20 minutes to give a polyurethane resin aqueous solution No. 9 (polyurethane resin molecular weight 22,000, acid value 2
9).

Comparative Production Example 2 The same apparatus as in Production Example 1 was used, and (Poly-3-
Methyl-1,5-pentane adipate) diol 240
Part, dimethylolpropionic acid 24.1 parts, and isophorone diisocyanate 71.1 parts were charged, and the reaction temperature was 90 ° C.
And reacted for 8 hours. After cooling to 60 ° C., 680 parts of water, 120 parts of isopropanol, and 18.0 parts of triethylamine were charged and water-solubilized.

Further, 10.9 parts of isophoronediamine,
0.5 part of hydrazine was added and reacted for 20 minutes to give a polyurethane resin aqueous solution No. 10 (molecular weight of polyurethane resin 22,000, acid value 2
9).

Comparative Production Example 3 Instead of 300 parts of (poly-3-methyl-1,5-pentaneadipate) diol having a molecular weight of 1500, a molecular weight of 5 was used.
Of poly (3-methyl-1,5-pentaneadipate) diol of 00, 300 parts of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride 29.4 parts to 147 parts of water and 740 parts of water. In 905 parts, isopropanol 131
Parts to 160 parts and triethylamine 20.2 parts to 101 parts
Polyurethane resin aqueous liquid No. 3 having a solid content concentration of 30% was manufactured by the same apparatus and method as in Production Example 1, except that the parts were changed.
11 (molecular weight of polyurethane resin 30,000,
Acid value 112).

[0093] Examples 1-11 and Comparative Examples 1 to 3 (aqueous printing ink composition) Polyurethane resin aqueous solution was fractionated by Preparative Example 1 to 8 and Comparative Production Examples 1 to 3 No. 1 to 11 were used and a water-based printing ink composition for lamination was produced according to the formulation shown in Table 1.

That is, the pigment and the aqueous solution of polyurethane resin were stirred for 45 minutes with a red devil type disperser, the cellulose resin and water were added, and the mixture was further stirred for 15 minutes.

Here, Fastgen Blue 5412SD (manufactured by Dainippon Ink and Chemicals, Inc.) was used as the pigment, and HEC SP-250 (manufactured by Daicel Chemical Industries, Ltd.) was used as the cellulose resin.

The re-solubility, adhesiveness and extrusion laminate strength of the obtained aqueous printing ink composition were evaluated by the following methods, and the results are shown in Table 1.

Immediately after production, the ink was in state A at 40 ° C.
The ink was allowed to stand for 1 month in the B state, and changes in each performance due to long-term storage of the ink were also observed.

(Re-solubility) Test Method After running for 10 seconds using the test ink composition with a gravure proofing machine, the operation was stopped and left as it was for 60 seconds. Then, it printed on the stretched polypropylene film (Toyobo Co., Ltd. make, P-2161, 30 micrometers, it calls the OPP film below), and the redissolvability of the ink was judged from the pitch number until it becomes a normal printed matter.

Evaluation Criteria A: Return to normal within 5 pitches B: Return to normal within 6 to 20 pitches C: Return to normal within 21 to 40 pitches D: Not return to normal even within 40 pitches (adhesiveness) The test ink composition was printed on a corona discharge-treated OPP film by a gravure proofing machine, a cellophane tape was attached to the printing surface, and the adhesiveness was evaluated from the degree to which the printed film peeled off from the film when it was rapidly peeled off. .

Evaluation Criteria A: The printed film does not peel from the film at all B: Less than 20% of the printed film area ratio peels from the film C: 20% or more and less than 50% of the printed film area ratio Peeled off from the film D: 50% or more as an area ratio of the printed film, peeled off from the film (extrusion laminating strength) Test method Each test ink composition was O
After printing on a PP film, an imine-based anchor coating agent (Toyo Morton Co., Ltd., EL-420) was applied, and molten polyethylene was laminated by an extrusion laminating machine to obtain a laminated product. These laminated products were cut at a temperature of 40 ° C. for 3 days and then cut into a width of 15 mm, and the T-type peel strength was measured using a peel tester manufactured by Yasuda Seiki Co., Ltd.

Evaluation method The actual value of the peel strength (g / 15 mm) was described.

[0102]

[Table 1]

From the results shown in Table 1, the aqueous printing ink composition using the polyurethane resin aqueous solution of the present invention has good redissolvability, high adhesiveness even after long-term storage, and laminate strength. On the other hand, the water-based printing ink composition using the conventional polyurethane resin water-based liquid given in the comparative example has decreased both the adhesiveness and the laminate strength when stored for a long period of time.

[0104]

EFFECT OF THE INVENTION Using the polyurethane resin aqueous liquid of the present invention
The water-based printing ink composition according to the present invention has good re-dissolvability, high adhesiveness even during long-term storage, and laminating suitability.

Continuation of the front page (56) Reference JP-A-6-184485 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 18/00-18/87 C09D 11/10

Claims (3)

(57) [Claims] 1. A organic diisocyanate component, a polymeric diol component and a chain extender, and further obtained by a reaction terminating agent are reacted optionally, and the following general formula (I) and (or) (II) A polyurethane resin having a structural unit represented by a number average molecular weight of 2,000 to 200,000 and an acid value of 5 to 100 is dissolved in water in the presence of a basic compound.
Or dispersed polyurethane resin aqueous solution and pigment
For laminating characterized by containing as an essential component
Aqueous printing ink composition . [Chemical 1] (In the formula, X represents —CH ₂ —, —CO— or —O—). 2. The water for laminating according to claim 1, wherein the polymer diol component has a structural unit represented by the general formula (I) and / or (II) in the molecule.
Printing ink composition . 3. The polyurethane resin has the general formula (I)
And / or (2) The total amount of carboxyl groups derived from the structural unit represented by (II) is contained in an amount of 30 mol% or more of the total carboxyl groups in the polyurethane resin molecule, and the aqueous laminating solution according to claim 1 or 2. Printing ink composition .