JP2008049706A - Aqueous urethane resin, aqueous printing ink composition, and packaging material using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous urethane resin which exhibits good adhesiveness and lamination properties even for a nonpolar plastic film, and also imparts good water resistance and boil resistance to the resultant ink film. <P>SOLUTION: The aqueous urethane resin (d) comprises three constituents of a compound (a) having a tertiary amino group and a functional group capable of reacting an isocyanate group in a same molecule, a compound (b) having a carboxyl group and a hydroxyl group in a same molecule, and an organic polyisocyanate (c). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a water-based urethane resin and a water-based printing ink composition, and a packaging material using the composition.

  In recent years, there has been an increasing demand for water-based printing inks in the printing ink industry from the standpoints of safety and health during work, environmental protection, and reduction of residual solvents in packaging materials. However, water-based printing inks have a problem that drying is slow compared with solvent-based inks, adhesion to a substrate and wettability are poor, and water resistance is low, resulting in poor boilability of laminated products. . Also, for plastic film substrates, water-based printing inks using water-based urethane resins are widely used from the viewpoint of versatility of adhesion, but their adhesion to polyolefin films such as polyethylene films and polypropylene films is low and practical. It was a big problem. As a means for improving the adhesion to a polyolefin film, JP-A-6-206972 discloses a urethane resin having a hydrazine residue in the molecule. It is thought that the hydrazine residue in the resin interacts with the functional group on the treated film surface and contributes to improving the adhesion to the film, but when introducing a hydrazine residue, a chain extender having a hydrazide group is used. The reactive hydrazine compound remains in the film, resulting in a decrease in water resistance. For this reason, problems such as delamination and blistering occur when ink and film surfaces are peeled off when the processed workpiece is boiled or retorted, and adhesion occurs depending on the processing method, processing degree, or change over time of the film. There was a drawback that the properties were likely to vary.

  Thus, it is difficult to improve the adhesion of water-based urethane resin to plastic films, especially adhesion to non-polar films such as polyolefin film, without impairing water resistance, boiling, retort suitability, etc. Met. For this reason, water-based printing inks that form films with excellent adhesion and water resistance in printing inks for laminating packaging materials that require boil resistance and retort resistance are strongly desired in the field of printing and packaging materials. It was.

  As a result of diligent efforts to solve the above-described problems, the present inventors have found that a water-based printing ink composition containing a specific water-based urethane resin has excellent adhesiveness to a polyolefin film and has water resistance. The present invention has been completed by finding that an ink film having excellent properties and laminating suitability can be obtained.

  That is, in the first invention, a compound (a) having a tertiary amino group and having a functional group capable of reacting with an isocyanate group in the same molecule, and a compound having a carboxyl group and a hydroxyl group in the same molecule ( An aqueous urethane resin (d) comprising at least three components, b) and an organic polyisocyanate (c).

  A second invention is the aqueous urethane resin (d) according to the first invention, wherein the functional group capable of reacting with the isocyanate group of the compound (a) is a hydroxyl group.

According to a third invention, the compound (a) is one or more selected from the group consisting of N-methyldiethanolamine and N, N-bis (2-hydroxypropyl) aniline. It is water-based urethane resin (d) as described in invention of this.

  4th invention is the water-based urethane resin in any one of 1st-3rd invention, wherein molar ratio a / b of a compound (a) and a compound (b) is 0.01-0.7 (D).

  5th invention is the water-based printing ink composition containing the water-based urethane resin (d) in any one of 1st-4th invention.

  6th invention is the packaging material formed by printing the water-based printing ink composition as described in 5th invention on a plastic film, and laminating.

  Since the water-based urethane resin of the present invention has a specific proportion of tertiary amino group and carboxyl group and has a structure having both flexibility and crosslinkability, the water-based printing ink of the present invention using the resin The composition exhibits adhesion to a plastic film, particularly good adhesion to a nonpolar plastic film, and the ink coating has good water resistance.

  Further, a packaging material obtained by printing the composition on a plastic film and laminating it has good laminating strength and boilability, and is particularly useful as a packaging material for food.

In the compound (a) having a tertiary amino group and a functional group capable of reacting with an isocyanate group in the same molecule used in the present invention, the functional group capable of reacting with the isocyanate group includes a hydroxyl group, amino Group, carboxyl group and the like. N- having two hydroxyl groups as a compound whose functional group capable of reacting with an isocyanate group is a hydroxyl group
Methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, Nt-butyldiethanolamine, dihydroxyisopropylethylamine, dihydroxyisopropyl n-butylamine, dihydroxyisopropyl t-butylamine, N, N-bis (2-hydroxypropyl) ) Aniline, and examples of the compound having one hydroxyl group include N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, and 3- (dimethylamino). Examples include 1-propanol, 3- (diethylamino) 1-propanol, hydroxyethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, and the like, or one or a combination of two or more thereof. Used in N-methyldiethanolamine and N, N-bis (2-hydroxypropyl) aniline are preferred from the viewpoint of the stability of the aqueous resin and the adhesiveness to the plastic film.

Examples of the compound in which the functional group capable of reacting with an isocyanate group is an amino group include N, N-bis (aminoethyl) methylamine, N, N-bis (aminopropyl) methylamine having two primary amino groups, N, N-bis (aminopropyl) ethylamine, N, N-dimethyl 1,3-diaminopropane having one primary amino group, N, N-diethyl 1,3-diaminopropane, N, N-diethylethylenediamine, N, N-dimethylethylenediamine etc. are mentioned, These are used alone or in combination of two or more.

  Examples of the compound (b) having a carboxyl group and a hydroxyl group in the same molecule used in the present invention include dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxy. Examples thereof include dimethylolalkanoic acid such as propionic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. In particular, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferable from the viewpoint of reactivity and solubility.

  The compound (b) contributes to making the urethane resin water-based. In addition to the compound (b), polyethylene glycol can be used as a component for making the urethane resin aqueous. If only this is used, the viscosity of the aqueous resin becomes extremely high, or the water resistance and boil resistance of the ink are increased. Sex is reduced. Moreover, when the water-based urethane resin which has a sulfonic acid group is used, the water resistance of ink will fall and all have a problem in practical use.

  The content of the compound (b) in the water-based urethane resin (d) is 3% by weight of the solid content of the water-based urethane resin (d) from the viewpoint of increasing the water-dispersing ability and increasing the pigment dispersion by increasing the water-dispersibility. In addition, from the viewpoint of increasing the water resistance of the ink, 20% by weight or less is preferable. When these carboxyl group-containing compounds are used, a self-emulsifiable urethane resin can be obtained.

In addition, the molar ratio a / b of the compound (a) and the compound (b) in the aqueous urethane resin (d) is 0.01 or more from the viewpoint of having good adhesion to a nonpolar plastic film,
From the viewpoint of the stability, water resistance and laminating suitability of the aqueous urethane resin (d), it is preferably 0.7 or less. In this range, a stable aqueous urethane resin is formed, and particularly excellent adhesion to the polyolefin film, good water resistance, and laminating suitability are exhibited.

  One of the reasons for having such excellent adhesiveness and ink film is that the urethane resin obtained in the present invention has a relatively soft skeleton, so it can also adhere to nonpolar plastic films. It is considered that toughness is developed at the same time because a cross-linked structure is formed by the interaction of acid / base in the molecule of the aqueous urethane resin and between the molecules.

In the present invention, a hydroxyl group-containing compound generally used for urethane synthesis can be used. For example, there are low molecular weight glycols having two hydroxyl groups in one molecule, high molecular weight glycols, polyols having three or more hydroxyl groups in one molecule, and the like. Low molecular weight glycols include diethylene glycol, trimethylene glycol, triethylene glycol,
Examples of propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, and the like, and those having two hydroxyl groups include 1,4 cyclohexane dimethanol and 1,4 cyclohexane diol.

  High molecular weight glycols include polyethers, polyesters, epoxies, and the like. Polyethers include polyethylene glycol, polyoxypropylene glycol, poly (ethylene / propylene) glycol, polytetramethylene glycol and the like. The polyester system is obtained by polycondensation of diol and dibasic acid. As the diol, in addition to the above-mentioned ethylene glycol and diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and dibasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid, Examples include terephthalic acid. In addition, examples of the high molecular weight compound having two hydroxyl groups include lactone ring-opening polymers such as polycaprolactone, poly β-methyl-δ-valerolactone, and polycarbonate.

  Examples of those having three or more hydroxyl groups include trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, and pentaerythritol. These polyols having three or more hydroxyl groups can be used as needed within a range in which the urethane resin does not gel.

  These hydroxyl group-containing compounds can be used alone or in combination of two or more. In order to balance the adhesiveness to the film substrate, the physical properties of the ink film, the water resistance, etc., it is generally necessary to use two or more types having different chemical structures, or to appropriately select their molecular weights. In the production of an aqueous urethane resin, when polyethylene glycol is used in combination, water-solubilization is facilitated, and a stable dispersion, hydrosol, and water-soluble resin can be obtained. The amount of polyethylene glycol used is preferably 1 to 20% by weight based on the solid content of the aqueous urethane resin. If it is less than 1% by weight, the stability of the aqueous resin is insufficient, and it is difficult to obtain a hydrosol or water-soluble resin unless the acid value of the resin is increased. On the other hand, if it exceeds 20% by weight, the viscosity may increase when it becomes water-based, and the water resistance of the ink may be poor.

  Examples of the organic polyisocyanate (c) used in the present invention include aromatic, aliphatic, and alicyclic bifunctional isocyanates and trifunctional isocyanates. Examples of the bifunctional isocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, hexa Methylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, 3, 3'-dimethyl-4, 4'-biphenylene diisocyanate, 3, 3'-dimethoxy- 4,4'-Buphenylene diisocyanate, 3,3'-Dichloro-4,4'-biphenylene diisocyanate, 1,5-naphtha Diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,5 (2,6) -bicyclo [2,2,1] heptanebis (isocyanatomethyl) (norbornane diisocyanate) and the like. It can be used in a combination of two or more species.

  Examples of trifunctional isocyanates include: 1) Adducts of trimethylolpropane, for example, Takenate D-160N (manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur HT (manufactured by Sumitomo Bayer Urethane Co., Ltd.), 2) Burette body, for example, Takenet D-165N (manufactured by Takeda Pharmaceutical Co., Ltd.), Sumijuur N3200 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), 3) isocyanurate ring type, for example, VESTANAT T1890 (manufactured by Huls) ) And the like. In the case of using a trifunctional isocyanate, it is particularly preferably 0.05 to 2% by weight of the solid content of the aqueous urethane resin (d) from the viewpoint of improving the cohesive force and controlling the viscosity during the reaction.

  The aqueous urethane resin (d) used in the present invention can be obtained by 1) an acetone method using an organic solvent, or 2) a solvent-free synthesis method using no solvent at all. In the latter case, since the viscosity is generally increased, it is necessary to devise a stirrer, a raw material composition and a chain extension method. Hereinafter, 1) the acetone method and 2) the solventless synthesis method will be described.

  1) Acetone method is a reaction in which viscosity is extremely high or a reaction that tends to be non-uniform, such as gelation, in particular, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate. This is a method of synthesis using an aromatic organic solvent such as a system solvent, toluene or xylene. Specifically, in the compound (a), when the functional group capable of reacting with an isocyanate group is an amino group, and even if it is other than an amino group, an amine compound, a hydrazide compound, a piperazine compound as a chain extender And the like are used, a urea bond is generated, so that the viscosity becomes extremely high and stirring or the like tends to be difficult. In addition, even in a reaction in which no urea bond is formed, the same thing occurs when a large amount of low molecular weight polyol is used. In such a case, when an organic solvent is used, the viscosity decreases, and the synthesis reaction can be performed uniformly and smoothly.

A catalyst is preferably used for the reaction between the isocyanate and the polyol compound. As the catalyst, a known metal catalyst or amine catalyst can be used. Examples of the metal catalyst include dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), 2-ethylhexoate lead, 2-ethylhexyl titanate, 2-ethylhexoate iron, 2- Examples thereof include ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, and tetra-n-butyltin. Examples of amine-based catalysts include tertiary amines such as tetramethylbutanediamine.

  The urethanization reaction is preferably performed at 50 to 100 ° C. for 10 minutes to 10 hours. The end point of the reaction is judged by viscosity measurement, NCO peak by IR measurement, NCO% measurement by titration, and the like.

  Chain extenders include ethylenediamine, hexamethylenediamine, aliphatic diamines such as 2,2,4 trimethylhexamethylenediamine, alicyclic diamines such as isophorone diamine, 1,4 diaminocyclohexane, malonic acid dihydrazide, succinic acid dihydrazide, glutar And hydrazide compounds such as acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide. Furthermore, polyamines such as diethylenetriamine and triethylenetetramine can be used within a range in which the urethane resin does not gel. In addition, glycols such as ethylene glycol, diethylene glycol, 1,3 propanediol and 1,4 butanediol can also be used.

  The chain extension reaction is preferably performed at 30 to 80 ° C. for 10 minutes to 10 hours. The end point of the reaction is judged by viscosity measurement, NCO peak by IR measurement, amine value measurement by titration, and the like.

  After obtaining a urethane resin having a predetermined molecular weight, it is preferable to neutralize the carboxyl group in the resin with a basic compound in order to make it aqueous. Basic compounds include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, Examples include triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, and morpholine. These are used alone or in combination of two or more. . Depending on the type of the basic compound, the compatibility with the polyurethane solution and the stability after being made into an aqueous solution may be different, so it is necessary to select them appropriately. Of these, ammonia is preferable from the viewpoints of water resistance, residual odor and the like of the printed matter.

  In neutralization of a compound having a carboxyl group such as dimethylolalkanoic acid, 0.4 to 1.2 equivalents are preferable with respect to 1 equivalent of the carboxyl group. As a method of making the urethane resin aqueous, there are a method of neutralizing with a base using the above-mentioned carboxyl group-containing diol, a method of using polyethylene glycol having a high water-solubilizing ability, and the like. In particular, when both are used in combination, a resin having a good balance between stability as a water-soluble resin and water resistance as an ink can be obtained.

  1) In the acetone method, it is necessary to remove the solvent depending on the type and amount of the solvent used. Solvent removal can be performed, for example, by adding water and a basic compound as a neutralizing agent to the reaction solution, and then raising the temperature and distilling the required amount of the solvent under normal pressure or reduced pressure.

  In compound (a), when the functional group capable of reacting with an isocyanate group is other than an amino group, and an amine-based chain extender is not used at the same time, no organic solvent is used depending on the resin composition. 2) Solvent-free synthesis The method can be used.

  In the solventless synthesis method, 1) the polyol and isocyanate may be charged from the beginning, or the isocyanate may be added after the polyol is charged. In the synthesis reaction, viscosity is generally a problem. Therefore, it is preferable to raise the temperature to such an extent that stirring is sufficiently possible and lower the viscosity. It is preferable to start the reaction in a uniform state by sufficiently dissolving and melting the resin raw material. If the reaction start temperature is low, or the compatibility between the resin raw materials and the raw material / generated resin is insufficient, a part of the raw materials are dispersed in the molten raw material, or the appearance becomes slightly opaque. Although it can be produced even in this state, when the reaction temperature is, for example, a polyol containing polyethylene glycol, a more uniform resin can be obtained even with less compatible diols if the reaction temperature is higher than the compatibility temperature. .

  The urethanization reaction is preferably performed at 90 to 200 ° C. for 10 minutes to 5 hours. The end point of the reaction is judged by viscosity measurement, NCO peak by IR measurement, NCO% measurement by titration, and the like.

The polyurethane resin is made water-based by neutralizing the carboxyl group with the aforementioned basic compound or water-solubilizing with polyethylene glycol or the like. When the reaction is carried out in the absence of a solvent, it is possible to make the aqueous solution using only water or a basic compound. However, the organic solvent has the function of converting the high-viscosity reaction product into a resin solution and smoothing the aqueous solution. Therefore, when an organic solvent is used as an auxiliary agent before making the polyurethane resin aqueous, it is easy to make it aqueous. To be done. At that time, it is possible to add directly after the synthesis of the polyurethane resin, or to add and dissolve the polyurethane resin in an organic solvent.

  When alcohol is used as the organic solvent, alcohol is generally used in combination with water-based printing inks. Examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl. Ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-n -Hexyl ether, 2, , 4-trimethylpentanediol-1,3-monoisobutyrate (Texanol, manufactured by Eastman Chemical Co., Ltd.), etc., and particularly isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, ethanol And methanol are preferred. These can be used alone or in combination of two or more. By appropriately selecting an alcohol suitable for the printing viscosity-dilutability, drying property, and film-forming property of the target printing ink from these alcohols, the solvent removal process can be omitted.

  The solvent-free synthesis method, which is the second method for obtaining an aqueous urethane resin, can greatly reduce the cost and the like generated by using a solvent, and therefore has great advantages in production and cost. In particular, when the amount of residual solvent in the printed matter is a problem, the proportion of the solvent removal process in the entire production process increases, which is a major factor in increasing the production cost of the aqueous urethane resin.

  The aqueous urethane resin of the present invention can be obtained by the above-described method, but a small amount of a surfactant can be used in combination for the purpose of improving the stability of the aqueous urethane resin. Surfactants include anionic surfactants such as fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, naphthalene sulfonates, and alkylsulfosuccinates; polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, Nonionic surfactants such as polyoxyethylene alkylphenyl ether and polyoxyethylene alkylphenyl ester are exemplified. In use, a method of adding in a state of being dissolved or dispersed in water or a mixture of water / basic compound, or a method of adding an alcohol to the alcohol when used as an auxiliary agent, etc. . The aqueous urethane resin thus obtained can be used in various forms such as emulsion, colloidal dispersion, water-soluble type, etc. depending on the resin composition, solvent composition, neutralization degree, etc.

The water-based printing ink composition of the present invention is a water-based urethane resin, if necessary, additives such as pigments, antifoaming agents, thickeners, leveling agents, UV absorbers, alcohol-based, ketone-based, ester-based It is composed of organic solvents such as As an example of the production, a pigment and an aqueous urethane resin are kneaded (for example, a ball mill, an attritor, a sand mill, etc.), and then additives and the like are mixed. In kneading, a pigment dispersant may be used as necessary. In addition to the aqueous urethane resin of the present invention, conventional aqueous urethane resins, polyester resins, acrylic resins, styrene-acrylic resins, styrene-maleic anhydride resins, rosin-modified maleic acid resins, cellulose resins, chlorinated polyolefins, etc. A combination of aqueous resins is also possible.

  The aqueous printing ink composition can be printed on a plastic film by a known gravure printing method or flexographic printing method.

  Examples of the plastic film include polyester, nylon, and polyolefin. In the case of a polyolefin film, a good printed matter can be obtained by using a surface-treated polyolefin film having a functional group such as a hydroxyl group or a carbonyl group.

The packaging material of the present invention is obtained by printing the water-based printing ink composition of the present invention on a plastic film and aging a laminated laminate product.
The laminating method is as follows: 1) Extrusion laminating method in which molten resin is laminated after applying an anchoring agent to the printed surface of the obtained printed matter, if necessary. 2) Applying an adhesive. Thereafter, a dry lamination method in which a plastic film is laminated by drying as necessary is exemplified.
As the molten resin, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used, and as the adhesive, imine, isocyanate, polybutadiene, titanate and the like can be mentioned.
The packaging material of the present invention is suitably used as a general packaging material, particularly a packaging material for food use.

The present invention will be specifically described below. In the following description, parts indicate parts by weight.
[Synthesis Example 1]
Poly (3-methylpentane adipate) having an average molecular weight of about 2,000 (hydroxyl value 55.9) in a four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer 163. 8 parts, 15.1 parts of polyethylene glycol having an average molecular weight of about 2,000 (hydroxyl value 56.3), 19.7 parts of dimethylolpropionic acid, and 0.3 parts of N-methyldiethanolamine were charged and replaced with dry nitrogen. The temperature was raised to 100 ° C. Under stirring, 51.0 parts of isophorone diisocyanate was added dropwise over 20 minutes, and the temperature was gradually raised to 140 ° C.
The reaction was further continued for 30 minutes to obtain a urethane resin. Next, 750 parts of distilled water containing 8.9 parts of aqueous ammonia was added while cooling to obtain an aqueous urethane resin (A) (molecular weight about 38,500).

[Synthesis Example 2]
111.0 parts of polytetramethylene glycol having an average molecular weight of about 2,000 (hydroxyl value 55.8), averaged in a four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas introduction pipe, a stirrer, and a thermometer 10.7 parts of polyethylene glycol having a molecular weight of about 2,000 (hydroxyl value 56.3), 4.3 parts of 1,4 cyclohexanedimethanol, 23 dimethylolbutanoic acid
. 4 parts, 0.1 part of dibutyltin dilaurate, and 200 parts of methyl ethyl ketone were charged, replaced with dry nitrogen, and heated to 80 ° C. Under stirring, 80.4 parts of isophorone diisocyanate was added dropwise over 20 minutes and reacted for 3 hours. The reaction product was cooled to 40 ° C., and a mixture consisting of 12.6 parts of N, N-bis (aminopropyl) methylamine, 7.7 parts of isophoronediamine, and 100 parts of methyl ethyl ketone was added dropwise over 30 minutes. The reaction was allowed to proceed for chain extension. Next, 880 parts of water and 9.6 parts of aqueous ammonia were added, the temperature was raised, 430 parts of the solvent was removed, and the solid content was adjusted to 25%, whereby an aqueous urethane resin (B) was obtained (molecular weight About 38,700).

  Table 1 shows the compositions of the aqueous urethane resins obtained in Synthesis Examples 1 to 12. Synthesis examples 3 to 10 were synthesized by the same method as synthesis example 1, and synthesis examples 11 and 12 were synthesized by the same method as synthesis example 2.

[Examples 1-10, Comparative Examples 1-2]
50 parts of an aqueous urethane resin (A to L), 15 parts of a phthalocyanine blue pigment (Lionol Blue-KLH manufactured by Toyo Ink Manufacturing Co., Ltd.), 0.1 part of an antifoaming agent, 5 parts of isopropyl alcohol, and 29.9 water The part was stirred for 10 minutes with an Eiger mill (manufactured by Eiger) to obtain an aqueous printing ink composition. The printing ink composition was adjusted to 16 seconds with Zarn Cup # 3 (manufactured by Kogaisha) using a mixed solvent of water / isopropyl alcohol = 1/1, and an aqueous printing ink composition for evaluation. Got.

In addition, the used water-based urethane resin is as follows.
Example 1 is an aqueous urethane resin (A),
Example 2 is an aqueous urethane resin (B),
Example 3 is an aqueous urethane resin (C),
Example 4 is an aqueous urethane resin (D),
Example 5 is an aqueous urethane resin (E),
Example 6 is an aqueous urethane resin (F),
Example 7 is an aqueous urethane resin (G),
Example 8 is an aqueous urethane resin (H),
Example 9 is an aqueous urethane resin (I),
Example 10 is an aqueous urethane resin (J),
Comparative Example 1 is an aqueous urethane resin (K),
Comparative Example 2 is an aqueous urethane resin (L).

  Polypropylene film (hereinafter referred to as OPP, “Pyrene P2161” manufactured by Toyobo Co., Ltd., thickness 20 μ), polyethylene terephthalate film (hereinafter referred to as PET, manufactured by Toyobo Co., Ltd.) A print sample was obtained by printing on “Ester E5100” (thickness: 15 μm), and the adhesion and water resistance were evaluated. For evaluation of extrusion laminating strength, an imine adhesive (EL420) manufactured by Toyo Motor Co., Ltd. is used for OPP printed materials, and an isocyanate anchor coating agent (Toyo Motor Co., Ltd.) for PET printed materials. -After the application of EL510 / CAT-RT80 manufactured by Ton Co., Ltd., lamination was performed using low-density polyethylene. In addition, about PET, the carbodiimide compound (Nisshinbo make, carbodilite V-02) which has the carbodiimide group of the same ratio as the carboxyl group in the printing ink prepared previously was added before printing. The processed PET laminate was aged at 40 ° C. for 2 days to obtain a sample for boil evaluation.

  The adhesiveness, water resistance, extrusion laminating strength, evaluation method of the boil test, and criteria are described below.

1) Evaluation of adhesiveness to OPP and PET films When the cellophane was affixed to the printing surface of a print sample and peeled off, the adhesiveness was evaluated by the degree to which the printed film peeled from the film surface.
◎ The printed film does not peel at all.
○ 20% or less of the printed film area is peeled off.
△ The area of more than 20% and less than 50% of the printed film peels.
× The area exceeding 50% of the printed film is peeled off.

2) Evaluation of water resistance After the print film of the print sample was rubbed 20 times with absorbent cotton soaked in water, the surface condition was visually observed.
◎ The printed film does not elute at all.
○ Less than 20% of the printed film area is eluted.
△ The area of more than 20% and less than 50% of the printed film is eluted.
× The area exceeding 50% of the printed film is eluted.

3) Evaluation of extrusion laminating strength The laminated product was cut into a width of 15 mm, and the T-type peel strength was measured.

4) Evaluation of boil resistance A PET laminate processed product was made into a bag, water was put inside and sealed, and then a boil test was performed at 95 ° C. for 30 minutes.
○ No delamination or blistering occurs.
△ Slight delamination and blistering occur.
× Considerable delamination and blistering.

Claims (8)

  A compound (a) having a tertiary amino group and a functional group capable of reacting with an isocyanate group in the same molecule; a compound (b) having a carboxyl group and a hydroxyl group in the same molecule; and an organic polyisocyanate. A water-based printing ink composition containing a urethane resin obtained by reacting at least three components in the absence of a solvent of (c) is printed on a polyethylene terephthalate, nylon, or polypropylene film, and further an adhesive or an anchor coating agent, and Laminated product obtained by sequentially laminating polyethylene films.   The laminate processed product according to claim 1, wherein the urethane resin has no urea bond.   The laminated product according to claim 1 or 2, wherein the functional group capable of reacting with the isocyanate group of the compound (a) is a hydroxyl group.   The laminated product according to any one of claims 1 to 3, wherein the compound (a) is at least one selected from the group consisting of N-methyldiethanolamine and N, N-bis (2-hydroxypropyl) aniline. .   The laminate processed product according to any one of claims 1 to 4, wherein the molar ratio a / b of the compound (a) to the compound (b) is 0.01 to 0.7.   The laminate processed product according to any one of claims 1 to 5, wherein the urethane resin is obtained by a urethanization reaction at 90 to 200 ° C.   The laminate processed product according to any one of claims 1 to 6, wherein the urethane resin is a water-based urethane resin (d) that has been made water-based with water, alcohol, and a neutralizing agent after the urethanization reaction.   A packaging material formed from the laminated product according to claim 1.