JP6743411B2 - Printing ink, method for producing polyurethane polyurea resin, and printed matter - Google Patents

Description

The present invention relates to a printing ink which comprises 95% by mass or more of a solvent composed of a single alcohol solvent and water and which is suitable for solvent recovery and reuse, which facilitates recovery of a volatile solvent during printing.

In the gravure ink used for printing plastic films for packaging materials such as confectionery and food, the polyurethane polyurea resin is mainly composed of a binder resin such as polyurethane polyurea resin, a pigment, a pigment dispersant and a solvent. There are two types of such gravure inks for packaging materials, organic solvent type and water-based type, and because of their characteristics such as high drying property, printing stability, and high physical properties of printed matter, 90% of gravure inks used for plastic films, etc. % Or more is organic solvent type gravure ink.

However, the organic solvent-type gravure ink involves a large amount of use and release of the organic solvent when used, and there is a concern that it may affect the environment. In recent years, problems related to atmospheric pollution such as destruction of the natural environment, ozone layer in the stratosphere, damage to agricultural products and destruction of forest resources due to acid rain in the lower stratosphere, and adverse effects on human body due to photochemical oxidants have been reported daily. It is getting serious, so enforcement of PRTR law to control chemical substance emission, strengthening of odor control law, reduction of carbon dioxide emission of Kyoto Protocol, air pollution prevention law, Saitama Prefectural Living Environment Conservation Ordinance, etc. Regarding the use of chemicals, regulations regarding the protection of the atmospheric environment have been tightened.

For this reason, the gravure printing industry is considering switching to an aqueous type as part of its efforts to protect the environment, but it has a low drying property and high surface tension, which is characteristic of water as a dispersion medium. The current situation is that the reduction of productivity and deterioration of quality due to the difficulty of redispersion of water-dispersible resins in water is unavoidable, and the transition in the industry has not progressed.

Under such circumstances, efforts are under study to burn or recover the organic solvent that has volatilized in the drying step after printing. However, the combustion process is not preferable from the viewpoint of preventing global warming because it produces a large amount of CO ₂ . On the other hand, as a means for recovering the organic solvent, the existing gravure ink uses a wide variety of organic solvents, so that there has been a problem that it is not easy to reuse and reuse the recovered solvent.

Therefore, the development of gravure ink that uses a single type of alcohol solvent that is easy to recover and reuse the organic solvent is progressing.For example, by introducing a branched structure into the molecular skeleton of polyurethane polyurea resin, the By using a resin with an oxyalkylene structure introduced as a binder resin, the solubility in alcoholic solvents such as isopropyl alcohol is improved, and in addition, there is a technology to prepare a gravure ink that is excellent in plate fog prevention and highlight transferability. It is known (see Patent Document 1 below).

However, in the gravure ink described in Patent Document 1, although the polyurethane polyurea resin itself used as the binder resin exhibits excellent solubility in alcoholic solvents, the urea bond concentration in the resin structure is as high as 1.2 mmol/g. However, the resin itself had a high cohesive force, the flexibility of the printed matter itself was impaired, the followability to the base film was poor, and sufficient laminate strength could not be obtained.

JP, 2013-194081, A

Therefore, the problem to be solved by the present invention is that the compatibility between the binder resin and the organic solvent when 95% by mass or more of the organic solvent component is composed of a single type of alcohol solvent is good, and the laminate strength is high. An object of the present invention is to provide an excellent printing ink, a binder resin used for the ink, and a printed matter printed by using the ink.

As a result of intensive studies to solve the above problems, the present inventors have found that as a binder resin for gravure ink, a urethane polyurea resin containing a polyether polyester structure site, and a polyurethane polyurea having a low urea bond concentration. We have found that the resin has excellent solubility in alcoholic solvents and excellent laminate strength when it is used as a printed material, and has completed the present invention.

That is, the present invention is a printing ink containing a polyurethane polyurea resin, a colorant, and an organic solvent, wherein the polyurethane polyurea resin contains a polyether polyester structure site in its resin structure and has a urea bond concentration of 0. .2 to 1.0 mmol/g, and the organic solvent contains a single type of alcohol solvent in a proportion of 95% by mass or more.

In the present invention, an alcohol component (a1) containing polyoxyalkylene glycol as an essential component and a polycarboxylic acid or its anhydride (a2) are further reacted to obtain a polyether polyester polyol (A) (step 1). Then, the obtained polyester polyol (A) is reacted with the polyvalent isocyanate (B) to obtain a urethane prepolymer (X) (step 2), and then the urethane prepolymer (X) and the monoamine (y1) ) And an amine component (Y) containing a diamine (y2) are reacted (step 3) with respect to the method for producing a polyurethane polyurea resin.

The present invention further relates to a printed matter obtained by printing using the printing ink.

According to the present invention, a printing ink having good compatibility with the binder resin and the organic solvent when 95% by mass or more of the organic solvent component is composed of a single type of alcohol solvent, and having excellent laminate strength, It is possible to provide a binder resin used for the ink, and a printed matter obtained by printing using the ink.

As described above, the polyurethane polyurea resin used in the printing ink of the present invention is characterized in that it contains the polyether polyester structure portion and the urea bond concentration is in the range of 0.2 to 1.0 mmol/g. In the present invention, by introducing a polyether polyester structure into the resin structure of the polyurethane polyurea resin, a high compatibility with an alcohol solvent having 95% by mass or more as a single species is exhibited, and the resin itself has an appropriate compatibility. It is possible to give excellent flexibility and cohesive force. Further, by setting the urea bond concentration low, the rigidity of the resin itself is suppressed and the laminate strength is dramatically improved. Here, the urea bond concentration of the polyurethane polyurea resin is the number of moles of urea bond in 1 g of the resin expressed in millimoles.

The polyurethane polyurea resin has a urethane bond concentration in the range of 0.500 to 1.500 mmol/g, but is preferable from the viewpoint that the resin itself has a good balance between appropriate cohesive force and flexibility. Here, the urethane bond concentration of the polyurethane polyurea resin is the number of moles of the urethane bond in 1 g of the resin expressed in millimoles. Here, the urea bond concentration and the urethane bond concentration of the polyurethane polyurea resin can be calculated from the reaction ratio of each raw material.

Here, the polyether polyester structure part in the polyurethane polyurea resin is a poly(polyester) obtained by reacting an alcohol component (a1) containing polyoxyalkylene glycol as an essential component with a polyvalent carboxylic acid or its anhydride (a2). It is a structural part derived from the ether polyester polyol (A), and has a polyether chain and an ester structure in the structure. The end of the structural portion has a structure in which a hydrogen atom is removed from the terminal hydroxyl group of the polyol (A), and is composed of an oxygen atom. In the polyurethane polyurea resin, a urethane bond is formed by the reaction between the polyether polyester polyol (A) and the polyvalent isocyanate (B). Therefore, the polyether polyester structural site is bonded to the nitrogen atom in the urethane bond. ing. Further, the urethane prepolymer (X) obtained by the reaction of the polyether polyester polyol (A) and the polyisocyanate (B) has an isocyanate group at the terminal of the resin structure thereof, which is a monoamine (y1) or A urea bond is formed by reacting with a diamine (y2).

That is, the polyurethane polyurea resin is reacted with an alcohol component (a1) containing polyoxyalkylene glycol as an essential component and a polyvalent carboxylic acid or its anhydride (a2) to obtain a polyether polyester polyol (A) (step 1) Then, the obtained polyester polyol (A) is reacted with the isocyanate component (B) containing diisocyanate as an essential component to obtain a urethane prepolymer (X) (step 2), and then the urethane prepolymer ( X) and the amine component (Y) containing the monoamine (y1) and the diamine (y2) are reacted (step 3).

Here, the polyoxyalkylene glycol (a1-1) that can be used as the alcohol component (a1) in Step 1 is an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran, for example, water, ethylene glycol, propylene glycol, Examples thereof include polyether polyols obtained by polymerization using a low molecular weight polyol such as trimethylolpropane and glycerin as an initiator.

Among these, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol are preferable because the finally obtained polyurethane polyurea resin has good compatibility with alcohol solvents. The number average molecular weight (Mn) of these polyoxyalkylene glycols is in the range of 100 to 1,000 because the coating adhesion is good, and thus a polyurethane polyurea resin having excellent solubility in an alcohol solvent can be obtained. In addition, the polyoxyalkylene chain does not become too long, the polyurethane polyurea resin exhibits appropriate rigidity, and an adhesive having excellent laminate strength is preferred.

In step 1, the alcohol component (a1) may be used in combination with other diol compounds (a1-2) in addition to the polyoxyalkylene glycol (a1-1). Specific examples of such other diol compound (a1-2) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3 propanediol, and 2-ethyl-. 2-butyl-1,3 propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5 pentanediol, hexanediol, octanediol, 1,4- Aliphatic diols such as butynediol may be mentioned.
Among these, 1,2-propanediol, 2-methyl-1,3 propanediol, 2-ethyl-, and the like, from the viewpoint that the finally obtained polyurethane polyurea resin has good compatibility with alcohol solvents. A branched alkylene diol having a side chain alkyl group having 3 to 10 carbon atoms such as 2-butyl-1,3 propanediol, 1,3-butanediol, neopentyl glycol, and 3-methyl-1,5 pentanediol. Is preferred.

The mass ratio [(a1-1)/(a1-2)] of the polyoxyalkylene glycol (a1-1) in the alcohol component (a1) to the other diol compound (a1-2) is 20. The ratio of /80 to 70/30 is preferable from the viewpoint of achieving a good balance between compatibility with alcohol solvents and flexibility and cohesive force of the resin itself.

Next, as the polyvalent carboxylic acid or its anhydride (a2) to be reacted with the alcohol component (a1) in step 1, adipic acid, succinic acid, oxalic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacine are used. Aliphatic dicarboxylic acids such as acids; unsaturated dicarboxylic acids such as maleic acid and fumaric acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid; phthalic anhydride, trimellitic acid Examples thereof include acid anhydrides such as acid anhydrides and pyromellitic acid anhydrides. Of these, an aliphatic dicarboxylic acid is preferable because a resin having excellent flexibility can be obtained.

The reaction ratio between the alcohol component (a1) and the polyvalent carboxylic acid or the anhydride thereof (a2) in step 1 is determined by the number of equivalents of hydroxyl groups in the alcohol component (a1) and the polyvalent carboxylic acid or anhydride thereof. The ratio [(a1)/(a2)] of the equivalent number of (a2) as the carboxylic acid is in the range of 1/0.88 to 1/0.95, so that the obtained polyether polyester (A) is It is preferable because the molecular weight can be easily adjusted to an appropriate range described later. In step 1, esterification can be carried out by a conventional method, but it is preferable to carry out the reaction under the temperature condition of 180 to 260° C. in the presence of an esterification catalyst, for example.

Examples of the esterification catalyst that can be used here include organic tin compounds, inorganic tin compounds, organic titanium compounds, and organic zinc compounds.

The polyether polyester polyol (A) thus obtained in step 1 has a weight average molecular weight (Mw) in the range of 2,500 to 5,000. This is preferable because the resin is imparted with appropriate flexibility and has excellent laminate strength and also has good solubility in an alcohol solvent. In particular, from the viewpoint of solubility in alcoholic solvents, the proportion of polyether structure sites in the polyether polyester polyol (A) is preferably in the range of 25 to 60 mass% based on the mass of the raw material.

Next, the polyester polyol (A) obtained in step 1 can be reacted with the polyisocyanate (B) to obtain the urethane prepolymer (X) (step 2).

Examples of the polyvalent isocyanate (B) used here include various known aromatic diisocyanates, aliphatic diisocyanates, and trifunctional to tetrafunctional polyisocyanates that are generally used in the production of polyurethane polyurea resins.

As the aromatic diisocyanate, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyl Diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane -Diisocyanate, 2,6-diisocyanate-benzyl chloride, and the like. Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene. Examples thereof include those having 1 to 9 carbon atoms such as diisocyanate. Examples of alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate. 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and the like. In addition, lysine diisocyanate, dimerisocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and the like can also be used as the diisocyanate.

Examples of the trifunctional or tetrafunctional polyisocyanates include adduct type polyisocyanates having a urethane bond site in the molecule and nurate type polyisocyanates having an isocyanurate ring structure in the molecule. These may be used alone or in combination of two or more.

The adduct-type polyisocyanate having a urethane bond site in the molecule is obtained, for example, by reacting a diisocyanate monomer with a trifunctional or higher functional polyhydric alcohol. Examples of the diisocyanate monomer used in the reaction include various diisocyanates exemplified as the above-mentioned diisocyanate, and they may be used alone or in combination of two or more kinds. Examples of the trifunctional or higher-functional polyhydric alcohol used in the reaction include trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol, which may be used alone or in combination of two or more kinds. You may do it.

Examples of the nurate type polyisocyanate having an isocyanurate ring structure in the molecule include those obtained by reacting a trimer of a diisocyanate monomer and a diisocyanate monomer with a monoalcohol or a dihydric alcohol. Examples of the diisocyanate monomer used here include various diisocyanate monomers exemplified as the above-mentioned diisocyanate, and they may be used alone or in combination of two or more kinds. The monoalcohol used in the reaction is hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptane. Decanol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyl dodecanol, 2-decyl tetradecanol, etc. are mentioned, and dihydric alcohols are ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propane. Diol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol , 3-methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis(hydroxymethyl)cyclohesane. ..

Of these, alicyclic diisocyanates are particularly preferred from the viewpoint of flexibility of the finally obtained polyurethane polyurea resin.

In the step 2, in the case where the above-mentioned polyether polyester polyol (A) and the polyvalent isocyanate (B) are reacted with each other, the reaction ratio between the two is such that the hydroxyl group (OH) in the polyol (A) and the polyvalent isocyanate (B) are The ratio (NCO/OH) to the isocyanate group (NCO) in () is preferably 1.2 to 3.0. When the ratio is less than 1.2, gelation may occur, and when it exceeds 3.0, the solubility of the prepolymer obtained tends to decrease.

The urethane prepolymer (X) thus obtained has an isocyanate residual ratio in the range of 1.00 to 5.00% by mass, and has a laminate strength of a printed matter finally obtained. It is preferable from the viewpoint of being excellent. Here, the isocyanate residual rate means that after taking out a part of the urethane prepolymer (X) sample and dissolving it in ethyl acetate, after adding an amine solution of a predetermined concentration and a predetermined amount, and then adding an indicator, The mass-based NCO group concentration is obtained by titration with hydrochloric acid.

After producing the urethane prepolymer (X) through step 2, then, in step 3, reacting the urethane prepolymer (X) and an amine component (Y) containing a monoamine (y1) and a diamine (y2). Thus, the desired polyurethane polyurea resin can be obtained.

In the amine component (Y), diamine acts as a chain extender and monoamine acts as a reaction terminator. In that case, the monoamine (y1) and the diamine (y2) are preferably compounds described below, and both the monoamine (y1) and the diamine (y2) are preferably compounds having a cyclohexane ring.

Examples of the diamine (y2) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Dicyclohexylmethane-4,4'-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxy Examples include ethylpropylenediamine, (N-aminoethyl)-2-ethanolamine, 2-hydroxypyropyrethylenediamine, di-2-hydroxypyropyrethylenediamine, and di-2-hydroxypropylethylenediamine.

Among these, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,2-cyclohexanediamine, or dicyclohexylmethane-4,4'-diamine (an amine having a cyclohexane ring) is preferable.

As the monoamine (y1), for example, a dialkylamine such as di-n-butylamine, a compound having an alicyclic hydrocarbon group such as N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine and cyclohexylethylamine, mono Examples thereof include alkanolamines such as ethanolamine, diethanolamine, and monoisopropanolamine. Among them, one or more compounds selected from the group consisting of N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and cyclohexylethylamine. However, it is preferable in that it gives good adhesion to the film or sheet substrate when used as a printing ink.

Further, in the present invention, a diamine or monoamine having a trialkoxysilyl group may be used in combination as the diamine (y2) or monoamine (y1). By using these, a trialkoxysilyl group is introduced into the molecular structure of the polyurethane polyurea resin, and a printing ink coating film obtained by using such a polyurea resin is preferable because it has high blocking properties. Examples of amines having such a trialkoxysilyl group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and N- 2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Etc. Among these, a monoamine having a trialkoxysilyl group is preferable, and 3-aminopropyltrimethoxysilane is more preferable, from the viewpoint that a polyurethane polyurea resin having a higher blocking property in a coating film when formed into an ink can be obtained.

Further, as the reaction terminator, alcohols such as ethanol and isopropyl alcohol may be used in combination, and when introducing a carboxyl group into the polyurethane polyurea resin, use an amino acid such as glycine or L-alanine as the reaction terminator. You can

As described above, the polyurethane polyurea resin described in detail above has a weight average molecular weight (Mw) in the range of 2,500 to 5,000, which is excellent in solubility in alcohol solvent components, and also has good laminate strength. It is also preferable because it is excellent.

Here, in the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column; Tosoh Corporation TSK-GUARDCOLUMN SuperHZ-L
+ Tosoh Corporation TSK-GEL SuperHZM-M×4
Detector; RI (differential refractometer)
Data processing: Multi-station GPC-8020 modelII manufactured by Tosoh Corporation
Measurement conditions; Column temperature 40°C
Solvent tetrahydrofuran
Flow rate 0.35 ml/min Standard; Monodisperse polystyrene sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)

The printing ink of the present invention is characterized by containing the detailed polyurethane polyurea resin, a colorant, and an organic solvent containing 95% by mass or more of a single type of alcohol solvent.

The above-mentioned "single type alcoholic solvent" means only one type of alcoholic solvent, and one type of alcoholic solvent and water, in which the existence ratio of water to the total of both is 50% by mass or less. It includes. When a mixture of one of the alcoholic solvents and water is used as the single type of alcoholic solvent, the content of water is preferably 20% by mass or less so that the amount of heat required for drying after printing is reduced. This is preferable from the viewpoint that the gravure printing can be performed at high speed.
The alcohol solvent used for the printing ink of the present invention is preferably one selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. In particular, ethanol, 1-propanol and 2-propanol are preferable from the viewpoints of drying speed, odor and safety for human body. If the proportion of water exceeds 50% by mass,
Further, "95% by mass or more of a single type of alcohol solvent" means that less than 5% by mass may use another type of alcohol solvent or may use another non-alcoholic solvent. This means that, in the present invention, it is preferable to use a single type of alcohol solvent at 100 mass% from the viewpoint of reuse and reuse of the solvent.

Examples of the colorant used in the present invention include white colorants, inorganic pigments other than white colorants, and organic colorants. Here, examples of the white colorant include organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like. Specific examples thereof include titanium oxide, zinc oxide, aluminum oxide, calcium carbonate, zinc sulfide, magnesium oxide, barium sulfate, magnesium sulfate, chromium oxide and silica. It is particularly preferable to use titanium oxide from the viewpoints of colorability, hiding power, chemical resistance, weather resistance and the like.

Examples of inorganic pigments other than white include pigments such as carbon black, aluminum, mica (mica), and red iron oxide (iron (III) oxide). Aluminum is generally in the form of powder or paste, but it is preferable to use it in the form of paste from the viewpoint of easy handling and safety to the human body, and a leafing or non-leafing type is used depending on the demand for brightness and density.

Examples of the organic colorant include organic pigments and dyes used in general inks, paints, recording materials and the like. For example, azo-based, phthalocyanine-based, dioxazine-based, quinacridone-based, anthraquinone-based, perinone-based, perylene-based, thioindigo-based, isoindolinone-based, quinophthalone-based, azomethineazo-based, diketopyrrolopyrrole-based, isoindoline-based pigments, etc. Can be mentioned.

The colorant is preferably contained in a proportion of 1 to 50 mass% with respect to the total mass of the printing ink in order to develop sufficient density and coloring power in the printing ink. Further, these colorants can be used alone or in combination of two or more kinds.

When the pigment is stably dispersed in the printing ink of the present invention, the resin alone can be dispersed, but a dispersant or a binder resin for dispersing the pigment can be used in combination for further stable dispersion of the pigment. For example, a cationic, anionic, nonionic, zwitterionic or other surfactant can be used. The amount of the dispersant used is preferably 0.05% by mass or more based on the total mass of the ink from the viewpoint of storage stability of the ink, and 5% by mass or less from the viewpoint of suitability for lamination. Furthermore, it is particularly preferable that the content is in the range of 0.1 to 2 mass %.

On the other hand, examples of the binder resin for pigment dispersion include vinyl chloride-vinyl acetate copolymer, hydroxypropyl cellulose, and nitrocellulose. Among these, for example, when ethanol which can be preferably used in the present invention is used as the alcohol solvent, hydroxypropyl cellulose is preferable because it has excellent solubility in ethanol.

These binder resins for pigment dispersion can be used by dissolving them in an organic solvent at a ratio of solid content of 1 to 30% by mass.

The printing ink of the present invention can be produced by dissolving or dispersing the above-mentioned polyurethane polyurea resin, colorant and the like in a single type of alcohol solvent. Specifically, a pigment dispersion is prepared by dispersing a pigment in an organic solvent with the resin and, if necessary, the dispersant, and the obtained pigment dispersion is blended with other compounds as necessary. By doing so, an ink can be produced.

The particle size distribution of the pigment dispersion can be optimized by appropriately adjusting the diameter of the grinding medium of the dispersion kneader, the filling rate, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. it can. As the disperser, a commonly used disperser such as a roller mill, a ball mill, a pebble mill, an attritor, or a sand mill can be used.

The viscosity of the printing ink produced by the above method is 10 mPa·s or more at the liquid temperature of the B-type viscometer of 25° C. from the viewpoint of preventing the pigment from settling and dispersing appropriately, and the workability efficiency at the time of ink production and printing is improved. From the viewpoint, the range is preferably 1000 mPa·s or less.

The printing ink of the present invention can be used in known printing methods such as gravure printing and flexographic printing. For example, it is diluted with a diluent solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or in a mixture.

The printing ink of the present invention can be made into a printed matter of the present invention by printing and applying it to various films and sheet-like substrates using the above-mentioned printing method, and drying and fixing by drying in an oven. .. Here, as the film and the sheet base material, polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resin such as polystyrene, AS resin and ABS resin, nylon, polyamide, Examples thereof include polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum and the like, or composite materials thereof.

The base material may be subjected to a vapor deposition coating treatment and/or a polyvinyl alcohol coating treatment on its surface, or may be further subjected to a surface treatment such as a corona treatment.

Furthermore, the usual extrusion lamination method in which a molten polyethylene resin is laminated on the printed surface of this printed matter through various anchor coating agents such as imine-based, isocyanate-based, polybutadiene-based, and titanium-based, urethane on the printed surface A laminated laminate using the printing ink of the present invention can be obtained by a known laminating process such as a laminating method of coating an adhesive such as a system and laminating plastic films.

Among these, a lamination method in which a urethane adhesive is applied to the printed surface and a plastic film is laminated is particularly preferable from the viewpoint of good lamination strength.

Here, the urethane-based adhesive includes a two-component adhesive of polyol/polyisocyanate, and the polyol component used here is obtained by reacting polyether polyol or the polyether polyol with polyisocyanate. Examples thereof include a polyether polyurethane polyol, a polyester polyol obtained by reacting a polybasic acid and a polyhydric alcohol, a polyester polyurethane polyol obtained by crosslinking the polyester polyol with a polyisocyanate, or a mixture of two or more thereof.

As the polyether polyol, in addition to diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, Ethylene oxide, propylene oxide, butylene oxide, styrene oxide with one or more compounds having two active hydrogen atoms such as 1,4-butanediol, 1,6-hexanediol and neopentyl glycol as an initiator Examples thereof include polyethers obtained by addition polymerization of one or more monomers such as epichlorohydrin, tetrahydrofuran and cyclohexylene.

The polyisocyanate used as a raw material for the polyether polyurethane polyol is aromatic diisocyanate such as diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate; 1,6-hexamethylene diisocyanate, 2,2,4- Linear aliphatic isocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate; isophorone diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, methylcyclohexylene diisocyanate, alicyclic such as isopropylidene dicyclohexyl-4,4′-diisocyanate Diisocyanate may be mentioned.

Next, as the polybasic acid which is the raw material of the polyester polyol, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2 -Bis(phenoxy)ethane-p,p'-dicarboxylic acid, anhydrides of these dicarboxylic acids, dimer acid and the like.

On the other hand, the polyhydric alcohol reacted with the polybasic acid is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5. -Pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, dimerdiol, hydrogenated bisphenol A, and other glycols.

Examples of the polyester polyurethane polyol include those obtained by reacting the polyester polyol with the polyisocyanate.

Among these, a polyether polyurethane polyol is preferable because it is excellent in flexibility as an adhesive and lamination strength.

On the other hand, as the polyisocyanate component to be combined with the polyol, aromatic diisocyanates such as diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate; 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexadiene Linear aliphatic isocyanates such as methylene diisocyanate and lysine diisocyanate; isophorone diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate,
Alicyclic diisocyanates such as methylcyclohexylene diisocyanate and isopropylidene dicyclohexyl-4,4'-diisocyanate; adducts obtained by adding 3 mol of organic diisocyanate to 1 mol of trimethylolpropane, and 3 mol of organic diisocyanate Burette obtained by reacting 1 mol of water, or polyfunctional organic polyisocyanate having a bond form such as isocyanurate obtained by polymerization of 3 mol of organic diisocyanate; polyisocyanate and polyester polyol, polyether polyol or, if necessary, A polyurethane polyisocyanate compound obtained by reacting these with a low-molecular polyol is mentioned.

The urethane-based adhesive described above is specifically a polyol component as a main component, a solvent-type adhesive diluted with a solvent using a polyisocyanate component as a curing agent, or a polyisocyanate component as a main component, and a polyol component as a main component. Any of solventless adhesives used as a curing agent may be used.

In the case of the solvent type, the solvent is used as a reaction medium during the production of the main agent and the curing agent, and is further used as a diluent during coating. Examples of usable solvents include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfamide and the like. Of these, it is usually preferable to use ethyl acetate.

The urethane adhesive is generally applied by a gravure roll coating method. The adhesive is applied in a solid content of 1.5 to 5 g/m ² , preferably ^{2 to 4} g/m ² under coating conditions. Usually, about 1.0~4.0g / ^{m 2} coating weight with a solvent type, it is preferred in the solvent-free in the range of about 0.5 to 3.0 g / ^{m 2.}

The printing ink of the present invention is characterized by using a single alcohol solvent and a polyurethane polyurea resin soluble in the alcohol, and an alcohol component can be easily separated and recovered from the solvent vapor generated in the printing and drying steps. .. The recovered solvent is a single alcohol, and unlike the case of an ester solvent, there are no by-products such as carboxylic acid, and the purification process can be simplified.

The present invention will be specifically described below with reference to examples. In addition, "part" and "%" in the examples are based on mass unless otherwise specified. The isocyanate residual ratio of the urethane prepolymer, which is an intermediate in each of the following Synthesis Examples and Comparative Synthesis Examples, was determined by sampling a portion of the urethane prepolymer and dissolving it in ethyl acetate, and then adding an amine solution of a predetermined concentration and a predetermined amount. Then, an indicator can be added and titrated with hydrochloric acid for measurement. Moreover, the number average molecular weight (Mn) and the weight average molecular weight (Mw) in each synthesis example and comparative synthesis example are the values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column; Tosoh Corporation TSK-GUARDCOLUMN SuperHZ-L
+ Tosoh Corporation TSK-GEL SuperHZM-M×4
Detector; RI (differential refractometer)
Data processing: Multi-station GPC-8020 modelII manufactured by Tosoh Corporation
Measurement conditions; Column temperature 40°C
Solvent tetrahydrofuran
Flow rate 0.35 ml/min Standard; Monodisperse polystyrene sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)

Further, various property values of the resins obtained in each of the synthetic examples and the comparative synthetic examples are obtained by the following methods.

Synthesis Example 1: Preparation of Polyurethane Polyurea Resin In a flask having a stirrer, a thermometer, and a rectification tube, 503.5 parts by mass of neopentyl glycol, a hydroxyl value of 280.5 (mgKOH/g), and a weight-average molecular weight of 400 polyoxy. Propylene glycol (Mitsui Chemicals Inc. “Actcoal D-400”) 466.2 parts by mass, adipic acid 620.3 parts by mass and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd. “Organics TA-10”) 0.07 parts by mass. A portion was charged, dry nitrogen was flown into the flask, and the mixture was heated to 200 to 250° C. with stirring to perform an esterification reaction. The reaction was stopped when the acid value became 0.5 mgKOH/g or less. The hydroxyl value of the obtained polyester diol was 102.2 mgKOH/g.

Next, 535.8 parts by mass of this polyester diol was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth-type reflux condenser, and a nitrogen gas inlet tube, and nitrogen gas was flowed and stirred. While raising the temperature to 50°C. Subsequently, 184.2 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 3.99% by mass, and a linear urethane having an aliphatic isocyanate group at both ends. A prepolymer (A1) was obtained.

Subsequently, 378.7 parts by mass of ethanol, 18.7-amino-3-aminomethyl-3, were added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 5,5-Trimethylcyclohexane 11.09 parts by mass, di-n-butylamine 1.09 parts by mass, and urethane prepolymer (A1) 150.1 parts by mass were added and reacted at 40° C. for 4 hours to give a solid content of 30%. A polyurethane polyurea resin solution (X1) was obtained which was an alcohol solution of the polyurethane polyurea resin (x1) having a weight average molecular weight of 20,000 and an amine value of 1.80 (mgKOH/g). Table 1 shows various property values of the obtained polyurethane polyurea resin (x1).

Synthesis Example 2: Preparation of Polyurethane Polyurea Resin)
In a flask having a stirrer, a thermometer, and a rectification tube, polyoxypropylene glycol having 285.4 parts by mass of neopentyl glycol, a hydroxyl value of 280.5 (mgKOH/g), and a weight average molecular weight of 400 (Mitsui Chemicals, Inc. Coal D-400") 790.0 parts by mass, adipic acid 455.0 parts by mass and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd. "Organics TA-10") 0.07 parts by mass are charged, and dry nitrogen is put in the flask. And the mixture was heated to 200 to 250° C. with stirring to carry out the esterification reaction. The reaction was stopped when the acid value became 0.5 mgKOH/g or less. The hydroxyl value of the obtained polyester diol was 111.9 mgKOH/g.

Next, 540.2 parts by mass of this polyester diol was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube, and nitrogen gas was flowed and stirred. While raising the temperature to 50°C. Subsequently, 180.5 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until NCO%, which is the residual ratio of isocyanate groups, reached 3.20% by mass, and a linear urethane having an aliphatic isocyanate group at both ends. A prepolymer (A2) was obtained.

Subsequently, 373.6 parts by mass of ethanol, 1-amino-3-aminomethyl-3, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas inlet tube. 5,5-Trimethylcyclohexane 9.01 parts by mass, di-n-butylamine 1.00 parts by mass, and urethane prepolymer (A2) 150.1 parts by mass were added and reacted at 40° C. for 4 hours to give a solid content of 30%. A polyurethane polyurea resin solution (X2) which is an alcohol solution of the polyurethane polyurea resin (x2) having a weight average molecular weight of 21,000 and an amine value of 1.80 (mgKOH/g) was obtained. Table 1 shows various property values of the obtained polyurethane polyurea resin (x2).

Synthesis Example 3: Preparation of Polyurethane Polyurea Resin)
In a flask having a stirrer, a thermometer, and a rectification tube, 502.7 parts by mass of neopentyl glycol, a hydroxyl value of 280.5 (mgKOH/g), and a weight average molecular weight of 400 polyoxyethylene glycol (NOF Corporation “PEG #400") 465.4 parts by mass, adipic acid 620.8 parts by mass, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd. "Organics TA-10") 0.07 parts by mass are charged, and dry nitrogen is flown into the flask. Then, the mixture was heated to 200 to 250° C. with stirring to carry out the esterification reaction. The reaction was stopped when the acid value became 0.5 mgKOH/g or less. The hydroxyl value of the obtained polyester diol was 114.3 mgKOH/g.

Next, 536.2 parts by mass of this polyester diol was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth-type reflux condenser, and a nitrogen gas inlet tube, and nitrogen gas was flowed and stirred. While raising the temperature to 50°C. Subsequently, 185.3 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 3.36%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was added. A polymer (A3) was obtained.
Subsequently, 114 parts by mass of ethanol, 1-amino-3-aminomethyl-3,5, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas inlet tube. 5.79 parts by mass of 5-trimethylcyclohexane, 1.25 parts by mass of di-n-butylamine, and 150.1 parts by mass of the urethane prepolymer (A3) were added and reacted at 40° C. for 4 hours to give a solid content of 30% and a weight of 30%. A polyurethane polyurea resin solution (X3) which is an alcohol solution of the polyurethane polyurea resin (x3) having an average molecular weight of 18,000 and an amine value of 1.80 (mgKOH/g) was obtained. Table 1 shows various property values of the obtained polyurethane polyurea resin (x3).

Synthesis Example 4: Preparation of polyurethane polyurea resin In a flask having a stirrer, a thermometer, and a rectification tube, 386.0 parts by mass of 2-methyl-1,3-propanediol, a hydroxyl value of 280.5 (mgKOH/g), and a weight average. 370.8 parts by mass of polyoxypropylene glycol having a molecular weight of 400 (“ACTCOL D-400” manufactured by Mitsui Chemicals, Inc.), 653.7 parts by mass of adipic acid and tetraisopropyl titanate (“Organics TA-10” manufactured by Matsumoto Fine Chemical Co., Ltd.) ) 0.07 parts by mass was charged, dry nitrogen was flown into the flask, and the mixture was heated to 200 to 250° C. with stirring to carry out the esterification reaction. The reaction was stopped when the acid value became 0.5 mgKOH/g or less. The hydroxyl value of the obtained polyester diol was 55.6 mgKOH/g.

Next, 170.6 parts by mass of this polyester diol was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth-type reflux condenser, and a nitrogen gas introduction tube, and nitrogen gas was flowed and stirred. While raising the temperature to 50°C. Subsequently, 42.61 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 4.23%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was introduced. A polymer (A4) was obtained.

Subsequently, 381.8 parts by mass of ethanol, 1-amino-3-aminomethyl-3, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 12.59 parts by mass of 5,5-trimethylcyclohexane, 0.94 parts by mass of di-n-butylamine, and 150.1 parts by mass of a urethane prepolymer (A4) were added and reacted at 40° C. for 4 hours to give a solid content of 30%. A polyurethane polyurea resin solution (X4) which is an alcohol solution of the polyurethane polyurea resin (x4) having a weight average molecular weight of 21,000 and an amine value of 2.10 (mgKOH/g) was obtained. Table 1 shows various property values of the obtained polyurethane polyurea resin (x4).

Synthesis Example 5: Preparation of polyurethane polyurea resin In a flask having a stirrer, a thermometer, and a rectification tube, 504.8 parts by mass of 2-butyl-2-ethyl-1,3-propanediol, a hydroxyl value of 280.5 (mgKOH /G), 490.1 parts by mass of polyoxypropylene glycol having a weight average molecular weight of 400 (“ACTCOL D-400” manufactured by Mitsui Chemicals, Inc.), 558.1 parts by mass of adipic acid and tetraisopropyl titanate (manufactured by Matsumoto Fine Chemical Co., Ltd. Organix TA-10") 0.07 parts by mass was charged, and dry nitrogen was flown into the flask and heated to 200 to 250°C with stirring to perform an esterification reaction. The reaction was stopped when the acid value became 0.5 mgKOH/g or less. The hydroxyl value of the obtained polyester diol was 35.3 mgKOH/g.
Next, 420.8 parts by mass of this polyester diol was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube, and nitrogen gas was flowed and stirred. While raising the temperature to 50°C. Subsequently, 55.4 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 1.98%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was added. A polymer (A5) was obtained.

Subsequently, 365.3 parts by mass of ethanol, 1-amino-3-aminomethyl-3, were added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 5,5-Trimethylcyclohexane 5.77 parts by mass, di-n-butylamine 0.70 parts by mass, and urethane prepolymer (A5) 150.1 parts by mass were added and reacted at 40° C. for 4 hours to give a solid content of 30%. A polyurethane polyurea resin solution (X5) which is an alcohol solution of the polyurethane polyurea resin (x5) having a weight average molecular weight of 30,000 and an amine value of 1.20 (mgKOH/g) was obtained. Table 1 shows various property values of the obtained polyurethane polyurea resin (x5).

Comparative Synthesis Example 1: Preparation of Polyurethane Polyurea Resin A 0.5 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser and a nitrogen gas inlet tube had a hydroxyl value of 112.2 (mgKOH). /G), 91.1 parts by mass of a condensate of 3-methyl-1,5-pentanediol and adipic acid having a weight average molecular weight of 1,000, a hydroxyl value of 112.2 (mgKOH/g), a weight average molecular weight of 1, 91.1 parts by mass of 000 polyoxypropylene glycol (“ACTCOL D-1000” manufactured by Mitsui Chemicals, Inc.) was charged, nitrogen gas was flown, and the temperature was raised to 50° C. with stirring. Subsequently, 80.1 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 5.72%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends ( B1) was obtained.
Subsequently, 686.0 parts by mass of ethanol, 1-amino-3-aminomethyl-3, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 31.32 parts by mass of 5,5-trimethylcyclohexane, 0.39 parts by mass of di-n-butylamine, and 262.3 parts by mass of a linear urethane prepolymer (B1) were added and reacted at 40° C. for 4 hours to give a solid content. A polyurethane polyurea resin solution (Y1), which is an alcohol solution of the polyurethane polyurea resin (y1) having a weight average molecular weight of 30,000 and an amine value of 3.00 (mgKOH/g), was obtained.

Comparative Synthesis Example 2: Preparation of Polyurethane Polyurea Resin A 0.5 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser and a nitrogen gas inlet tube had a hydroxyl value of 112.2 (mgKOH). /G), 91.1 parts by mass of a condensate of neopentyl glycol having a molecular weight of 1,000 and adipic acid, a hydroxyl value of 112.2 (mgKOH/g), and a polyoxypropylene glycol having a molecular weight of 1,000 (manufactured by Mitsui Chemicals, Inc.). (Actcole D-1000)) 91.1 parts by mass was charged, nitrogen gas was flown, and the temperature was raised to 50° C. with stirring. Then, 80.1 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 5.72%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was added. A polymer (B2) was obtained.
Subsequently, 686.0 parts by mass of ethanol, 1-amino-3-aminomethyl-3, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 31.32 parts by mass of 5,5-trimethylcyclohexane, 0.39 parts by mass of di-n-butylamine, and 262.3 parts by mass of the linear urethane prepolymer (B2) were added and reacted at 40° C. for 4 hours to give a solid content. A polyurethane polyurea resin solution (Y2), which is an alcohol solution of the polyurethane polyurea resin (y2) having a weight average molecular weight of 30,000 and an amine value of 3.00 (mgKOH/g), was obtained. Various property values of the obtained polyurethane polyurea resin (y1) are shown in Table 1.

Comparative Synthetic Example 3: Preparation of Polyurethane Polyurea Resin A hydroxyl value of 112.2 (mgKOH was added to a 0.5 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth-type reflux condenser and a nitrogen gas inlet tube. /G), and 182.2 parts by mass of polyoxypropylene glycol having a weight average molecular weight of 1,000 (“ACTCOL D-1000” manufactured by Mitsui Chemicals, Inc.) were charged, and nitrogen gas was flown therein, and the temperature was raised to 50° C. with stirring. .. Then, 80.1 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 5.72%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was added. A polymer (B3) was obtained.
Subsequently, 686.0 parts by mass of ethanol, 1-amino-3-aminomethyl-3, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 31.32 parts by mass of 5,5-trimethylcyclohexane, 0.39 parts by mass of di-n-butylamine, and 262.3 parts by mass of a linear urethane prepolymer (B3) were added and reacted at 40° C. for 4 hours to give a solid content. A polyurethane polyurea resin solution (Y3) having a 30% weight average molecular weight of 30,000 and an amine value of 3.00 (mgKOH/g), which was an alcohol solution of the polyurethane polyurea resin (y3), was obtained. Table 1 shows various property values of the obtained polyurethane polyurea resin (y3).

Comparative Synthesis Example 4: Preparation of Polyurethane Polyurea Resin Hydroxyl value was 56.1 (mgKOH) in a 0.5 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser and a nitrogen gas inlet tube. /G), 20.2 parts by mass of a condensate of 3-methyl-1,5-pentanediol and adipic acid having a weight average molecular weight of 2,000, a hydroxyl value of 112.2 (mgKOH/g), a weight average molecular weight of 1, 158.8 parts by mass of polyoxypropylene glycol (“Actcole D-1000” manufactured by Mitsui Chemicals, Inc.) of 000 was charged, and nitrogen gas was flowed, and the temperature was raised to 50° C. with stirring. Subsequently, 81.1 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 5.65%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was added. A polymer (B4) was obtained.
Subsequently, 686.9 parts by mass of ethanol, 1-amino-3-aminomethyl-3, were added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 5,5-Trimethylcyclohexane (30.62 parts by mass), di-n-butylamine (0.39 parts by mass), and linear urethane prepolymer (B4) (263.4 parts by mass) were added and reacted at 40° C. for 4 hours to cause gelation. Came to.

Comparative Synthesis Example 5: Preparation of Polyurethane Polyurea Resin A hydroxyl value of 112.2 (mgKOH was added to a 0.5-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser and a nitrogen gas inlet tube. /G), 99.8 parts by mass of a condensate of 3-methyl-1,5-pentanediol and adipic acid having a weight average molecular weight of 1,000, a hydroxyl value of 280.5 (mgKOH/g), and a weight average molecular weight of 400. 99.8 parts by mass of polyoxypropylene glycol (“ACTCOL D-400” manufactured by Mitsui Chemicals, Inc.) was charged, nitrogen gas was flown, and the temperature was raised to 50° C. with stirring. Subsequently, 155.1 parts by mass of isophorone diisocyanate was added and reacted at 90° C. until the residual rate of isocyanate groups, NCO%, reached 9.45%, and a linear urethane prepolymer having aliphatic isocyanate groups at both ends was added. A polymer (B5) was obtained.
Subsequently, 992.0 parts by mass of ethanol, 1-amino-3-aminomethyl-3, in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube. 69.84 parts by mass of 5,5-trimethylcyclohexane, 0.59 parts by mass of di-n-butylamine, and 354.7 parts by mass of a linear urethane prepolymer (B5) were added and reacted at 40° C. for 4 hours to give a solid content. A polyurethane polyurea resin solution (Y5) having an alcohol content of 30%, a weight average molecular weight of 25,000, and an amine value of 3.70 (mgKOH/g) was obtained. Table 1 shows various property values of the obtained polyurethane polyurea resin (y5).

Comparative Synthesis Example 6: Preparation of Polyurethane Polyurea Resin A four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas inlet tube was charged with polyoxypropylene glycol (“Act Coal” manufactured by Mitsui Chemicals, Inc.). D-3000" weight average molecular weight (Mw) 3,000, hydroxyl value 37.4 mgKOH/g) 148 parts by mass, polyoxytetramethylene glycol (Hodogaya Chemical Co., Ltd. "PTG-L2,000" weight average molecular weight (Mw) 2,000, hydroxyl value 56.1 mgKOH/g) 49 parts by mass, polycaprolactone diol containing ε-caprolactone as a main component ("Placcel 220EB" manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight (Mw) 2,000, hydroxyl value 56.1 mg KOH/g) 49 parts by mass, polyoxyethylene glycol monomethyl ether (“NOIOX M-1000” manufactured by NOF CORPORATION, weight average molecular weight (Mw) 1,000, hydroxyl value 56.1 mg KOH/g) 62 parts by mass. , 1,1,1-trimethylolpropane was added in an amount of 5 parts by mass, and the temperature was raised to 50° C. with nitrogen gas flow while stirring. Next, 112 parts by mass of isophorone diisocyanate was charged, and 0.021 parts by mass of zinc octylate was added as a catalyst. The temperature was further raised to 90° C., and the reaction was carried out until the isocyanate group content became 4.8% by mass to obtain a polyurethane prepolymer.

Then, into a four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas inlet tube, 1120 parts by mass of isopropyl alcohol, 49 parts by mass of isophoronediamine, and 5 parts by mass of dinormal butylamine were charged. The temperature was raised to 40°C. Next, 426 parts by mass of the polyurethane prepolymer obtained in the previous step was charged and reacted at 40° C. for 4 hours to obtain an alcohol solution of a polyurethane polyurea resin (y6) having a solid content of 30% by mass and an amine value of 2.94 mgKOH/g. A polyurethane polyurea resin solution (Y6) was obtained.
Table 1 shows various property values of the obtained polyurethane polyurea resin (y6).

Examples 1-5, Comparative Examples 1-4
10 parts by mass of hydroxypropyl cellulose (“NISSO HPC” manufactured by Nippon Soda Co., Ltd., an ethanol solution having a nonvolatile content of 15% by mass) as a binder resin for dispersing pigments, the polyurethane polyurea resin solution [X1 to X5, Y1 to Y3 and Y5] 25 parts by mass, a black pigment (“Regal 99R” manufactured by Cabot Corp.) 10 parts by mass, and ethanol 25 parts by mass were mixed with stirring and kneaded using a bead mill. An ink composition was obtained by further mixing 20 parts by mass of a polyurethane polyurea resin solution and 20 parts by mass of ethanol with the composition after kneading.
[Laminated adhesive strength] and [Boil resistance] were evaluated by the following methods. The results are shown in Tables 2 and 3. [Ethanol solubility] was evaluated using the polyurethane polyurea resin solution obtained in each of the above Synthesis Examples and Comparative Synthesis Examples.

[Laminated adhesive strength]
The ink composition obtained in each Example or Comparative Example was applied to the corona discharge treated surface of a biaxially stretched polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd., thickness 12 μm). Next, 16 parts by mass of an ether-based urethane adhesive (“Dicdry LX-401A”/“SP-60” manufactured by DIC Graphics Co., Ltd.) was applied to the surface of the coating at a coating amount of 3.0 g/m ^2. did. A linear low-density polyethylene film (“TUX-HC” manufactured by Mitsui Chemicals Tohcello Co., Ltd., “TUX-HC” thickness 60 μm) as a sealant was overlaid on the adhesive-coated film, and laminated and bonded. This laminated laminate was allowed to stand in a constant temperature bath at 40° C. for 72 hours, aged, and then air-cooled to room temperature, and the laminated laminate was cut into a tape having a width of 15 mm. Using a tensile tester ("Tensilon RTM-25" manufactured by Orientec), a peeling test was performed at a tensile speed of 300 mm/min in a state where the sealant was bent into 180 degrees or a T-shape, and the strength was recorded. At that time, the higher the peel strength, the more desirable.

[Boile resistance]
The above laminated laminate was made into a bag, a mixture of water/salad oil/meat sauce was added as a content, and after sealing and heating at 100° C. for 60 minutes, the presence or absence of lami floating was visually judged by appearance. The criteria for judgment are as follows.
○: There is no floating lami.
×... Delamination occurred.

[Ethanol solubility]
50 g of the polyurethane polyurea resin solution obtained in each of the synthesis examples and the comparative synthesis example was placed in a 100 ml glass bottle and the appearance was determined. The criteria for judgment are as follows.
○: colorless and transparent ×: cloudy

Comparative Example 5
25 parts by mass of the polyurethane polyurea resin solution (Y6) obtained in Comparative Synthesis Example 6, 10 parts by mass of a red pigment (“SYMULER RED 3090” manufactured by DIC Corporation), and 25 parts by mass of isopropyl alcohol were stirred and mixed, and kneaded using a bead mill. I had meat.
An ink composition was obtained by further mixing 20 parts by mass of the polyurethane polyurea resin solution (Y6) and 20 parts by mass of isopropyl alcohol with the composition after kneading.
Using the adjusted ink composition, [laminate adhesive strength] and [boil resistance] were evaluated in the same manner as in Example 1. The results are shown in Table 3. The [ethanol solubility] was evaluated using the polyurethane polyurea resin solution (Y6).

Claims (6)

A method for producing a printing ink containing a polyurethane polyurea resin, a colorant, and an organic solvent,
The polyurethane polyurea resin is
An alcohol component (a1) containing polyoxyalkylene glycol as an essential component and a polyvalent carboxylic acid or an anhydride thereof (a2) are reacted to obtain a polyether polyester polyol (A) (step 1), and then obtained. The polyester polyol (A) and the polyvalent isocyanate (B) are reacted to obtain a urethane prepolymer (X) (step 2), and then the urethane prepolymer (X), and a monoamine (y1) and a diamine (y2). A polyurethane polyurea resin obtained by a method of reacting an amine component (Y) containing (step 3) ,
The resin structure contains a polyether polyester structure portion, has a urea bond concentration of 0.2 to 1.0 mmol/g, and the organic solvent is a single kind of alcohol solvent in an amount of 95% by mass or more. A method for producing a printing ink , which is included in the following ratio . The method for producing a printing ink according to claim 1, wherein the polyoxyalkylene glycol used as the alcohol component (a1) in the step 1 has a weight average molecular weight (Mw) of 100 to 1,000. The method for producing a printing ink according to claim 1 or 2, wherein the polyether polyester polyol (A) has a weight average molecular weight (Mw) of 2,500 to 5,000. The monoamine (y1) is one or more compounds selected from the group consisting of N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and cyclohexylethylamine. Printing ink manufacturing method. The diamine (y2) is 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,2-cyclohexanediamine, or dicyclohexylmethane-4,4'-diamine. A method for producing the printing ink according to any one of items. A method for producing a printed matter obtained by printing using the printing ink obtained by the production method according to claim 1.