WO2015041022A1 - Printing ink and printed material - Google Patents

Abstract

Provided are the following: a printing ink in which 95 mass % or more of solvent components are constituted from a single type of alcohol-based solvent and water and the ink exhibits good drying properties, printing stability and physical properties, thereby facilitating during printing the recovery of volatile solvents and a reduction in the number of trapping defects caused by ink permeation; and printed material obtained by printing with this printing ink. The printing ink contains a polyurethane-polyurea resin, a coloring agent and a single type of alcohol-based solvent, wherein the polyurethane-polyurea resin is a resin obtained by reacting, as essential components, a polyurethane prepolymer (X) which is obtained by reacting an alcohol component having a polyoxyalkylene glycol (A) as an essential component with an isocyanate component having a diisocyanate as an essential component, and an amine component (Y) that contains a monoamine (y1) having an alicyclic hydrocarbon group and a diamine (y2).

Description

Printing ink and printed matter

The present invention relates to a printing ink suitable for solvent recovery and reuse in which 95% or more of the solvent is composed of a single alcohol solvent and water, and the volatile solvent can be easily recovered during printing.

In recent years, air pollution problems such as destruction of the natural environment, destruction of the 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 bodies due to photochemical oxidants have become serious every day. It has become. For this reason, laws related to air environment conservation such as the enforcement of the PRTR Law to prevent this, the strengthening of regulations on the Odor Prevention Law, the reduction of carbon dioxide emissions under the Kyoto Protocol, the Air Pollution Control Law, the Saitama Prefecture Living Environment Conservation Ordinance, etc. It is getting stricter. In particular, in the gravure printing industry that uses and releases a large amount of organic solvents, interest in solvent recovery and reuse is increasing as a means to solve these problems.

In fact, in the field of laminating adhesives and publishing gravure printing, the solvent species is designed to have a composition of toluene alone, and the volatile solvent is recovered and reused. This is because the recovery solvent can also be obtained with a single composition if it is a single solvent composition and can be easily reused as a diluting solvent for adhesives and inks.

There are two types of gravure inks mainly used in the manufacture of soft packaging materials: organic solvent type and water-based type. Among them, 90% or more of gravure inks used for plastic films and the like are organic solvent type inks. This is because the drying property, printing stability, and physical properties are high, and there are excellent characteristics as compared with the aqueous type. On the other hand, reduction of organic solvents is required in recent efforts for environmental protection. However, when switching to the water-based type, the low drying property and high surface tension peculiar to water, which is the dispersion medium, and the decrease in productivity due to the fact that the water-dispersed resin is difficult to re-disperse in water. , The deterioration of quality is inevitable, and the transition in the industry is not progressing.

Under such circumstances, an approach to burn or recover the organic solvent volatilized in the drying process after printing has been studied. However, the combustion treatment generates a large amount of CO _2, which is not preferable from the viewpoint of preventing global warming. Therefore, although recovery processing is expected to become the mainstream, the current gravure ink uses a wide variety of organic solvents, so that it is not easy to reuse and reuse the recovered solvent.

Therefore, efforts have been made to promote recovery and reuse by limiting the types of organic solvents. For example, an ink is disclosed that includes two types of organic solvents, an ester solvent, an alcohol solvent, and water as main components and is easy to recover (for example, see Patent Document 1). However, there are few alcohol components and there exists a tendency for it to be inferior to storage stability. Also, although inks limited to three solvents of ester, ketone and alcohol have been introduced, the difficulty of purification remains. In particular, ketone solvents are easily colored during recovery, and it is difficult to reuse the recovered solvent (for example, see Patent Document 2).

An ester solvent frequently used as one of organic solvents produces carboxylic acid as a by-product during the recovery and in the distillation / purification process after recovery. In general, when carboxylic acid remains as it is, the pH of the printing ink solution is lowered, and not only the ink physical properties such as printing suitability and ink coating adhesion are reduced, but also the work in the printing process due to its unique and harmful odor. It causes serious damage to the health of employees, and also tends to cause odor problems due to trace components remaining in the printed matter. Therefore, in the purification process, the carboxylic acid must be completely removed.

However, it is extremely difficult to completely remove the carboxylic acid in the distillation process that is generally used, and even if possible, it is very expensive. Therefore, the operation cost is lower than that of a conventional gravure ink composed of a plurality of types of organic solvents. There is a problem that becomes high. This problem can be solved by using a printing ink consisting of an alcohol solvent that does not use an ester solvent that is a source of carboxylic acid, but the conventional polyurethane polyurea resin that is the main binder of printing ink is only an alcohol solvent. However, it is difficult to achieve both sufficient solubility, printing stability and physical properties.

95% or more with two types of organic solvents that do not contain water and are composed of normal propyl acetate (NPAC) and isopropyl alcohol (IPA), or two types of ethyl acetate (EA) and isopropyl alcohol (IPA) Occupied and easy to collect inks are also known, but the solubility of the solvent is low and the resin design is limited. (For example, refer to Patent Document 3). Also known are two-component inks of normal propyl acetate (NPAC) and normal propyl alcohol (NPA), and two-component inks of ethyl acetate (EA) and normal propyl alcohol (NPA). There are some difficulties (see, for example, Patent Document 4 and Patent Document 5). Nowadays, it is further required to reduce the types of alcohol solvents.

In addition, if the solubility in a single type of alcohol solvent is excessively increased, there is a problem that a trapping defect in which the ink penetrates when the ink is overprinted is generated.

JP-A-7-247456 JP-A-9-328646 JP 2008-019427 A JP 2008-266370 A JP 2008-265032 A

The problem to be solved by the present invention is that 95% by mass or more of the solvent component is composed of a single kind of alcohol solvent and water, and in addition to high drying properties, printing stability, and physical properties, It is an object of the present invention to provide a printing ink that is easy to collect and that reduces the trapping defect that the ink soaks in, and a printed matter that is printed using the ink.

As a result of intensive studies to solve the above problems, the present inventor further obtained a polyurethane prepolymer obtained by reacting polyoxyalkylene glycol and diisocyanate, an amino group-containing chain extender having an alicyclic hydrocarbon group, and It has been found that an ink containing a polyurethane polyurea resin obtained by reacting with a reaction terminator can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention relates to a printing ink containing a polyurethane polyurea resin, a colorant, and a single type of alcohol solvent, wherein the polyurethane polyurea resin comprises an alcohol component and a diisocyanate containing polyoxyalkylene glycol (A) as essential components. It is obtained by reacting a polyurethane prepolymer (X) obtained by reacting with a monoamine (y1) having an alicyclic hydrocarbon group and an amine component (Y) containing a diamine (y2) as essential components. The present invention relates to a printing ink that is a resin.

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

According to the present invention, as a volatile component, a printing ink in which only a single type of alcohol solvent is a main component of an organic solvent, drying property, printing stability, physical properties are good, and trapping defects into which ink penetrates are reduced. Is obtained. Generally, the solvent recovered after printing is recovered in a form in which moisture in the atmosphere is mixed. Even if this recovered liquid is simply distilled, it is distilled in the form of an azeotrope of alcohol and water, so that it is necessary to go through a multistage precision distillation process in order to completely remove the water. The printing ink of the present invention is an alcohol / water mixed ink, and the solvent can be reused in the state of an azeotropic mixture of alcohol and water, resulting in a large cost merit.

The polyurethane polyurea resin used in the printing ink of the present invention has a polyurethane prepolymer (X) obtained by reacting an alcohol component containing polyoxyalkylene glycol (A) as an essential component with diisocyanate, and an alicyclic hydrocarbon group. This resin is obtained by reacting monoamine (y1) and amine component (Y) containing diamine (y2) as essential components.

Here, as the polyoxyalkylene glycol (A) constituting the alcohol component used in producing the polyurethane prepolymer (X), for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, And polyether polyols obtained by polymerization using a low molecular weight polyol such as ethylene glycol, propylene glycol, trimethylolpropane and glycerin as an initiator. Among these, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol are particularly preferable. The number average molecular weight (Mn) of these polyoxyalkylene glycols (A) is preferably 400 or more from the viewpoint of good film adhesion, and is preferably 4,000 or less from the viewpoint of good film heat resistance.

In addition to the polyalkylene glycol (A), a polyester diol (B) can be used as necessary as the alcohol component.

Examples of the polyester diol (B) that can be used here include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-ethyl-2butyl-1 , 3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, , 4-Butylenediol, diethylene glycol, triethylene glycol, polypropylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentae One or more types of saturated or unsaturated low molecular weight polyols such as lithol, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimeline Polyester polyols obtained by dehydration condensation or polymerization of polycarboxylic acids such as acid, peric acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid or the like or their anhydrides are preferably used. The number average molecular weight (Mn) of the polyester diol (B) is preferably 400 or more because the coating film adhesion is good, and it is 1,500 or less because the solubility in an alcohol solvent is good. preferable.

When the polyester diol (B) is used as the alcohol component, the amount of the polyester diol (B) used is determined by the composition ratio of the polyoxyalkylene glycol (A) and the polyester diol (B) [(A) / (B) ( The mass ratio is preferably in the range of 100/0 to 20/80. Furthermore, the composition ratio is particularly preferably in the range of 100/0 to 70/30 because of good solubility in an alcohol solvent.

Further, in the present invention, as the alcohol component, in addition to the polyalkylene glycol (A), a monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure can be used. Here, the monoalcohol (C) is used in combination with a tri- to tetra-functional polyhydric alcohol (D) described later as an alcohol component, or used in combination with a tri- to tetra-functional polyisocyanate described later as an isocyanate component. This is preferable because a polyoxyalkylene structure can be introduced into the side chain of the finally obtained polyurethane polyurea resin, and the solubility in an alcohol solvent and the printability are good.

The monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure used here is, for example, polyoxyethylene glycol such as polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monoethyl ether, polyoxyethylene glycol monopropyl ether, etc. Monoalkylene ether; polyoxypropylene glycol monomethyl ether, polyoxypropylene glycol monoethyl ether, polyoxypropylene glycol monoalkyl ether such as polyoxypropylene glycol monopropyl ether; polyoxybutylene glycol monomethyl ether, polyoxybutylene glycol monoethyl ether Polyoxybutylene such as polyoxybutylene glycol monopropylene ether A recall monoalkylene ether; a monoalkylene ether of glycol having two or more kinds of polyoxyalkylene chains selected from the group consisting of a polyoxyethylene chain, a polyoxypropylene chain, and a polyoxytetramethylene chain in the molecular structure. It is done. These may be used alone or in combination of two or more. Among these, it is highly soluble in alcohol-based solvents, resists plate fog when used in printing inks, has good highlight transferability, and is stable when moisture is mixed from the air during printing. Polyoxyethylene glycol monomethyl ether, polyoxypropylene glycol monomethyl ether, and monomethyl ether of glycol having both a polyoxyethylene chain and a polyoxypropylene chain in the molecular structure are preferable. More preferred is a monomethyl ether of glycol having both a polyoxyethylene chain and a polyoxypropylene chain.

The number average molecular weight (Mn) of the monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure is highly soluble in alcohol solvents, and is difficult to cause plate fog when used in printing inks. Since a polyurethane polyurea resin having good transferability and good stability when water is mixed from the air during printing is obtained, it is preferably in the range of 300 to 5,000, Is more preferably in the range of 000, and particularly preferably in the range of 550 to 2,000.

Further, the hydroxyl value of the monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure is highly soluble in alcohol solvents, hardly causes plate fogging when used in printing ink, and has a highlight transferability. Is obtained, and a polyurethane polyurea resin having good stability when moisture is mixed from the air during printing is obtained. Therefore, it is preferably in the range of 22 to 370 mgKOH / g, preferably 28 to 220 mgKOH / g. The range is more preferable, and the range of 56 to 205 mgKOH / g is particularly preferable.

When the monoalcohol (C) having a polyoxyalkylene skeleton is used as the alcohol component, the amount of the monoalcohol (C) used is 100 parts by mass of the raw material component of the polyurethane prepolymer (X) in the molecular structure. When the content of the monoalcohol (C) is in the range of 5 to 65 parts by mass, the solubility in alcoholic solvents is high, and when used in printing ink, plate fog hardly occurs, and highlight transition It is preferable because a polyurethane polyurea resin having good properties and stability when water is mixed from the air during printing is obtained, and more preferably in the range of 10 to 55 parts by mass.

Here, as described above, as the alcohol component used as a raw material of the polyurethane prepolymer (X), the polyoxyalkylene glycol (A), the monoalcohol (C), and a tri- to tetrafunctional polyhydric alcohol ( It is preferable to use D) together.

That is, the polyurethane polyurea resin used in the present invention increases the solubility in an alcohol solvent, realizes high storage stability that can be stably stored in an alcohol solvent for a long period of time, and when used in a printing ink, The polyoxyalkylene glycol (A) is used as the raw material alcohol component in order to improve the stability against moisture mixed from inside. However, when a large amount of polyoxyalkylene skeleton is introduced into the main chain of the polyurethane polyurea resin, the solubility in alcohol solvents and the stability due to moisture mixing when used in printing inks are improved, but blocking resistance, laminate Adhesive strength is reduced.

Therefore, in the present invention, as a raw material of the polyurethane polyurea resin, a monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure and a tri- to tetrafunctional polyhydric alcohol (D) are used. By introducing a polyoxyalkylene skeleton as a chain, it is highly soluble in alcoholic solvents, resists plate fog when used in printing ink, has excellent highlight transferability, and has blocking resistance and laminate adhesive strength. In addition, it is possible to improve the stability when moisture is mixed from the air during printing, and the pigment dispersibility of the finally obtained printing ink is also improved.

Therefore, the polyurethane polyurea resin used in the present invention comprises an alcohol component containing a polyester diol (A), a monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure, and a tri- to tetrafunctional polyhydric alcohol (D). A polyurethane prepolymer (X) obtained by reacting an isocyanate component containing diisocyanate as an essential component, and an amine component (Y) containing a monoamine (y1) having an alicyclic hydrocarbon group and a diamine (y2). A resin obtained by reaction is preferred.

Such tri- to tetrafunctional polyhydric alcohols (D) are, for example, trimethylolethane, trimethylolpropane, 1,2,3-propanetriol, 1,2,5-pentanetriol, 1,3,5-cyclohexane. Examples thereof include polyhydric alcohols such as triol, 1,2,9-nonanetriol, glycerin, erythritol and pentaerythritol, and polyoxyalkylene ethers thereof. These may be used alone or in combination of two or more. Among these, a polyurethane polyurea resin that has high solubility in alcohol solvents, is less likely to cause plate fog when used in printing ink, and has good stability when moisture is mixed in from the air during printing is obtained. Therefore, a polyhydric alcohol having 6 or less carbon atoms is preferable, and trimethylolpropane is more preferable.

The amount of the tri- to tetra-functional polyhydric alcohol (D) used is in the range of 0.1 to 20 parts by mass in 100 parts by mass of the raw material component of the polyurethane prepolymer (X). When it is used in printing ink, it is hard to cause plate fogging, has excellent highlight transferability, has excellent blocking resistance and laminate adhesive strength, and has moisture mixed in from the air during printing However, it is preferable from the viewpoint of obtaining a polyurethane polyurea resin having good stability, and more preferably in the range of 0.3 to 15 parts by mass.

In the present invention, a diol compound may be used in combination with the alcohol component in addition to the above (A), (B), (C), and (D). Specific examples of the diol compound include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 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, Examples thereof include neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis (hydroxymethyl) cyclohesan and the like.

Of these, ethylene glycol and 1,4-butanediol are particularly preferred from the viewpoint of good solubility of the finally obtained polyurethane polyurea resin in an alcohol solvent. The amount of these diol compounds used is in the range of 0.5 to 10% by mass in the alcohol component, since the solubility in an alcohol solvent can be improved without impairing the effects of the present invention. preferable.

Next, the diisocyanate, which is an essential component of the isocyanate component to be reacted with the polyurethane prepolymer (X), includes various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like that are generally used in the production of polyurethane polyurea resins. Can be mentioned. Here, aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate. , Tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloro Methyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, etc. Examples of the diisocyanate include those having 1 to 9 carbon atoms such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Diisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate. , Lysine diisocyanate, dimer acid carboxyl group Dimer diisocyanate and the like which is converted to isocyanate groups. These diisocyanate compounds can be used alone or in admixture of two or more.

In the present invention, as the isocyanate component, a tri- to tetra-functional polyisocyanate may be used in combination with the isocyanate component. By using the tri- to tetra-functional polyisocyanate in combination, a branched structure is formed in the polyurethane polyurea resin, and by using together with the monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure of the alcohol component, the final structure is obtained. A polyoxyalkylene skeleton can be introduced into the side chain of the polyurethane polyurea resin obtained. Thereby, the solubility to an alcohol solvent and printability become favorable. Examples of the tri- to tetrafunctional polyisocyanate 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 polyisocyanate having a urethane bond site in the molecule can be obtained, for example, by reacting a diisocyanate monomer with a trifunctional or higher polyhydric alcohol. Examples of the diisocyanate monomer used in the reaction include various diisocyanates exemplified as the diisocyanate, and each may be used alone or in combination of two or more. Examples of the trifunctional or higher polyhydric alcohol used in the reaction include trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, etc., each of which may be used alone or in combination of two or more. You may do it.

Examples of the nurate type polyisocyanate having an isocyanurate ring structure in the molecule include a trimer of a diisocyanate monomer and a product obtained by reacting a diisocyanate monomer with a monoalcohol and / or a dihydric alcohol. . Examples of the diisocyanate monomer used herein include various diisocyanate monomers exemplified as the diisocyanate, and each may be used alone or in combination of two or more. Monoalcohols used in the reaction are hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hepta. Decanol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, 2-decyltetradecanol and the like, and dihydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propane. Diol, , 2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3- Examples include methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and 1,4-bis (hydroxymethyl) cyclohesan. These monoalcohols and dihydric alcohols may be used alone or in combination of two or more.

Among these, the solubility in alcoholic solvents is high, the plate fog hardly occurs when used in printing ink, the highlight transferability is good, and the stability when moisture is mixed from the air during printing is also good. Since a good polyurethane polyurea resin can be obtained, the nurate type polyisocyanate is preferable, and in particular, a nurate body which is a trimer of the aliphatic diisocyanate is more preferable.

The content of the tri- to tetrafunctional polyisocyanate is highly soluble in alcoholic solvents, hardly causes plate fog when used in printing ink, has good highlight transferability, anti-blocking properties and laminate adhesion. A polyurethane polyurea resin having excellent strength and having good stability even when moisture is mixed in from the air during printing can be obtained. Therefore, in 100 parts by mass of the raw material component of the polyurethane prepolymer (X), 0.1 to 20 The range is preferably in the range of parts by mass, and more preferably in the range of 0.3 to 15% by mass.

In the present invention, as means for introducing a polyoxyalkylene chain into the side chain of the polyurethane polyurea resin, the monoalcohol (C) and the tri- to tetrafunctional polyhydric alcohol (D) are used in combination, or the monoalcohol ( C) and tri- or tetrafunctional polyisocyanate can be used in combination. However, in the present invention, the solubility in alcoholic solvents is higher, and when used in printing ink, plate fog is less likely to occur. A polyurethane polyurea resin with good stability and good stability when moisture is mixed in from the air during printing, and also has excellent pigment dispersibility and adhesion when used as printing ink. From the standpoint of expression, the monoalcohol (C) and the tri- to tetrafunctional polyhydric alcohol (D) are preferably used in combination.

The polyurethane prepolymer (X), which is a precursor of the polyurethane polyurea resin used in the present invention, reacts an alcohol component having the polyoxyalkylene glycol (A) as an essential component and an isocyanate component having a diisocyanate as an essential component. The reaction ratio of the two is such that the ratio (NCO / OH) of the hydroxyl group (OH) in the alcohol component to the isocyanate group (NCO) in the isocyanate component is 1.2-3. 0 is preferred. When the ratio is less than 1.2, gelation may occur. When the ratio is more than 3.0, the solubility of the resulting prepolymer tends to decrease.

The polyurethane polyurea resin used in the present invention is obtained by reacting the polyurethane prepolymer (X) with an amine component (Y) containing a monoamine (y1) and diamine (y2) having an alicyclic hydrocarbon group. is there. In the amine component (Y), diamine functions as a chain extender and monoamine functions as a reaction terminator. In that case, the monoamine (y1) and the diamine (y2) are preferably compounds described later, 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 Ethyl propylene diamine, (N-aminoethyl) -2-ethanolamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2- Amines having a hydroxyl group in the molecule, such as mud propyl ethylene diamine.

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

Examples of the monoamine (y1) include compounds having an alicyclic hydrocarbon group such as dialkylamines such as di-n-butylamine, N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and cyclohexylethylamine. However, it is essential to include a compound having the alicyclic hydrocarbon group. Among these, N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and adhesion to a film or sheet substrate when one or more compounds of the group consisting of cyclohexylethylamine are used as printing inks. Is preferable from the point that becomes favorable.

Furthermore, 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, but a printing ink coating film obtained using such a polyurea resin is preferable because it has high blocking properties. Examples of such an amine having a trialkoxysilyl group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 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 in that a polyurethane polyurea resin having a higher blocking property can be obtained when the coating film is converted into an ink.

Furthermore, alcohols such as ethanol and isopropyl alcohol may be used together as a reaction terminator. When a carboxyl group is to be introduced into a polyurethane polyurea resin, an amino acid such as glycine or L-alanine is used as a reaction terminator. Can do.

The polyurethane polyurea resin described in detail above has a weight average molecular weight (Mw) in the range of 10,000 to 80,000 because the solubility in the solvent component and the effect of preventing trapping failure are good. Further, the range of 15,000 to 50,000 is preferable from the viewpoint that these performance balances are good.

Here, the number average molecular weight (Mn) of the polyoxyalkylene glycol (A), the number average molecular weight (Mn) of the polyester diol (B), and the number average of the monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure. The molecular weight (Mn) and the weight average molecular weight (Mw) of the polyurethane polyurea resin are values measured by gel permeation chromatography (GPC) under the following conditions.

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

The printing ink of the present invention is characterized by containing the detailed polyurethane polyurea resin, a colorant, and a single kind of alcohol solvent.

The single type alcohol solvent used here is a total of 95% by mass or more of the single type alcohol solvent and water, and the mass ratio of the alcohol solvent to water [alcohol solvent / water] is 50. : 50 to 100: 0. More preferably, the mass ratio [alcohol solvent / water] is in the range of 80:20 to 100: 0. The alcohol solvent used in 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 viewpoint of drying speed, odor, and safety to human body. If the water ratio is more than 50% by mass, the amount of heat required for drying after printing increases, and gravure printing at high speed becomes difficult.

Also, examples of the colorant used in the present invention include a white colorant, an inorganic pigment other than a white colorant, and an organic colorant. Here, examples of the white colorant include organic and inorganic pigments and dyes used in general inks, paints, and recording agents. Specific examples include titanium oxide, zinc oxide, aluminum oxide, calcium carbonate, zinc sulfide, magnesium oxide, barium sulfate, magnesium sulfate, chromium oxide, and silica. In particular, it is preferable to use titanium oxide from the viewpoints of colorability, hiding properties, chemical resistance, weather resistance, and the like.

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

Examples of organic colorants include organic pigments and dyes used in general inks, paints, and recording agents. For example, pigments such as azo, phthalocyanine, dioxazine, quinacridone, anthraquinone, perinone, perylene, thioindigo, isoindolinone, quinophthalone, azomethine azo, diketopyrrolopyrrole, isoindoline, etc. Can be mentioned.

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

When the pigment is stably dispersed in the printing ink of the present invention, the resin alone can be dispersed, but a dispersant can be used in combination for further dispersing the pigment stably. For example, cationic, anionic, nonionic, amphoteric surfactants can be used. The amount of the dispersant used is preferably 0.05% by mass or more with respect to the total mass of the ink and 5% by mass or less from the viewpoint of laminate suitability from the viewpoint of the storage stability of the ink. Further, it is particularly preferably contained in the range of 0.1 to 2% by mass.

The printing ink of the present invention can be produced by dissolving or dispersing the above-described polyurethane polyurea resin, colorant and the like in a single kind of alcohol solvent. Specifically, a pigment dispersion in which a pigment is dispersed in an organic solvent with the resin, and if necessary, with the dispersant is manufactured, and other compounds are blended with the obtained pigment dispersion as necessary. Thus, an ink can be produced.

The particle size distribution of the pigment dispersion can be optimized by appropriately adjusting the diameter of the grinding media of the dispersion grinder, 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, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

The viscosity of the printing ink produced by the above method is 10 mPa · s or more at a liquid temperature of B-type viscometer at 25 ° C., from the viewpoint of preventing the precipitation of the pigment and dispersing it appropriately. From the viewpoint, it is preferably in the range of 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 mixed.

The printing ink of the present invention can be made into a printed material of the present invention by applying printing and coating on various films and sheet-like substrates using the above printing method, and drying and fixing by oven drying. . Here, as the film and sheet substrate, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide, Polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, or a composite material thereof can be given.

The base material may be subjected to vapor deposition coating treatment and / or polyvinyl alcohol coating treatment on the surface of metal oxide or the like, and may further be subjected to surface treatment such as corona treatment.

Furthermore, the usual extrusion lamination (extrusion laminating) method in which molten polyethylene resin is laminated on the printed surface of the printed material through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printed surface The printing ink of the present invention was used by a known laminating process such as a dry laminating method in which an adhesive such as a system is applied and a plastic film is laminated, or a direct laminating method in which a molten polypropylene is directly pressed and laminated on a printing surface. Laminate laminate is obtained

The printing ink of the present invention is characterized by using a single alcohol solvent and a polyurethane polyurea resin that is soluble in the alcohol, and can easily separate and recover alcohol components from solvent vapor generated in printing and drying processes. . The recovered solvent is a single alcohol, and unlike the ester solvent, there is no by-product such as carboxylic acid, and the purification process can be simplified.

Hereinafter, the present invention will be specifically described with reference to examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the number average molecular weight (Mn) and the weight average molecular weight (Mw) in each of the following synthesis examples and comparative synthesis examples are values measured by gel permeation chromatography (GPC) under the following conditions.

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

(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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 191,000 parts of polyethylene glycol of 1,000, was charged, and the temperature was raised to 50 ° C. while stirring and flowing nitrogen gas. Subsequently, 75.1 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 4.3%, and both ends were linear urethane prepolymers (A1 )
Subsequently, 700 parts of ethanol, 1-amino-3-aminomethyl-3,5,5-5-liter in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube were used. 24.0 parts of trimethylcyclohexane and 1.8 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 274.2 parts of a linear urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 40,000, an amine value of 1.2 (mgKOH / An alcohol solution (X1) of polyurethane polyurea resin of g) was obtained. Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 2: Preparation of polyurethane polyurea resin)
Polyethylene glycol having a hydroxyl value of 280.5 (mgKOH / g) and a number average molecular weight (Mn) of 400 in a four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube. 3 parts were charged, nitrogen gas was passed, and the temperature was raised to 50 ° C. with stirring. Subsequently, 130.2 parts of isophorone diisocyanate was added and reacted at 90 ° C. until NCO%, which is the residual ratio of isocyanate groups, reached 10.0%, and both ends were linear urethane prepolymers (A2 )
Subsequently, 700 parts of ethanol, 1-amino-3-aminomethyl-3,5,5-5-liter in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas inlet tube were used. 47.2 parts of trimethylcyclohexane and 5.3 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 247.5 parts of linear urethane prepolymer (A2) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 20,000, an amine value of 1.2 (mgKOH / An alcohol solution (X2) of polyurethane polyurea resin of g) was obtained. Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 3: 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 has a hydroxyl value of 37.4 (mgKOH / g) and a number average molecular weight (Mn) of 3 Then, 247.7 parts of polyethylene glycol of 1,000 was charged, and nitrogen gas was allowed to flow, and the temperature was raised to 50 ° C. while stirring. Subsequently, 36.7 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 2.4%, and both ends were linear urethane prepolymers (A3 )
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. After adding 14.1 parts of 5-trimethylcyclohexane and 1.5 parts of cyclohexylamine, the temperature was raised to 40 ° C. Next, 284.4 parts of linear urethane prepolymer (A3) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 57,000, an amine value of 1.2 (mgKOH / An alcohol solution (X3) of polyurethane polyurea resin of g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 4: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 198.1 parts of 1,000,000 polyethylene glycol was charged, and the temperature was raised to 50 ° C. while stirring under nitrogen gas. Subsequently, 74.7 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 4.3%, and both ends were linear urethane prepolymers (A4 ) Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 23.8 parts of 5-trimethylcyclohexane and 3.4 parts of dicyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 272.8 parts of a linear urethane prepolymer (A4) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 42,000, an amine value of 1.2 (mgKOH / An alcohol solution (X4) of polyurethane polyurea resin of g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 5: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Was charged with 204.1 parts of polyethylene glycol, heated to 50 ° C. with nitrogen gas flow and stirring. Subsequently, 77.0 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 4.3%, and both ends were linear urethane prepolymers (A5 )
Subsequently, 700 parts of 2-propanol, 16.5 parts of 1,2-cyclohexanediamine, 1-part of 2-propanol were added to a 2-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction pipe. 2.4 parts of n-butylamine was added and the temperature was raised to 40 ° C. Next, 281.1 parts of linear urethane prepolymer (A5) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 44,000, an amine value of 1.2 (mgKOH / An alcohol solution (X5) of polyurethane polyurea resin of g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 6: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Polyethylene glycol having a molecular structure of 180.8 parts of polyethylene glycol having a hydroxyl value of 28.4 (mgKOH / g) and a number average molecular weight (Mn) of 2,000, and a monomethyl ether of glycol having polyoxyethylene and polyoxyproprene in the molecular structure 17.4 parts and 1.2 parts of 1,1,1-trimethylolpropane were charged, and the temperature was raised to 50 ° C. while flowing nitrogen gas and stirring. Subsequently, 74.9 parts of isophorone diisocyanate was added, and the reaction was continued at 90 ° C. until NCO%, which is the residual ratio of isocyanate groups, reached 4.3%. A linear urethane prepolymer (A6) obtained by graft polymerization was obtained.
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 5-Trimethylcyclohexane 23.9 parts and cyclohexylamine 1.8 parts were added, and the temperature was raised to 40 ° C. Next, 274.3 parts of a linear urethane prepolymer (A6) in which a hydrophilic site is graft-polymerized on the side chain is added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 41, An alcohol solution (X6) of polyurethane polyurea resin having an amine value of 000 and an amine value of 1.2 (mgKOH / g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 7: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Polyethylene glycol 42.2 parts, hydroxyl value 28.4 (mgKOH / g), number average molecular weight (Mn) 2,000 monomethyl ether of glycol having polyoxyethylene and polyoxypropylene in the molecular structure 149.3 parts and 10.1, 1 part of 1,1,1-trimethylolpropane were charged, and the temperature was raised to 50 ° C. while flowing nitrogen gas and stirring. Subsequently, 73.0 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 4.1%. A linear urethane prepolymer (A7) obtained by graft polymerization was obtained.
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 21.6 parts of 5-trimethylcyclohexane and 3.8 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 274.6 parts of a linear urethane prepolymer (A6) in which a hydrophilic site is graft-polymerized on the side chain is added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 29, An alcohol solution (X7) of polyurethane polyurea resin having an amine value of 000 and an amine value of 1.2 (mgKOH / g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 8: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Condensation product of 3-methyl-1,5-pentanediol and adipic acid having a polyethylene glycol of 159.3 parts, a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1,000. 8 parts were charged, nitrogen gas was passed, and the temperature was raised to 50 ° C. with stirring. Subsequently, 75.1 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 4.3%, and both ends were linear urethane prepolymers (A8 )
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 24.0 parts of 5-trimethylcyclohexane and 1.8 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 274.2 parts of a linear urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 40,000, an amine value of 1.2 (mgKOH / An alcohol solution (X8) of polyurethane polyurea resin of g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 9: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Polyethylene glycol 36.9 parts having a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1,000, a condensate of 3-methyl-1,5-pentanediol and adipic acid. 7 parts were charged, nitrogen gas was passed, and the temperature was raised to 50 ° C. with stirring. Subsequently, 81.9 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 5.8%, and both ends were linear urethane prepolymers (A9 )
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 31.7 parts of 5-trimethylcyclohexane and 1.8 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 266.5 parts of linear urethane prepolymer (A1) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 42,000, an amine value of 1.2 (mgKOH / An alcohol solution (X9) of polyurethane polyurea resin of g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 10: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Condensate of 3-methyl-1,5-pentanediol and adipic acid having a polyethylene glycol of 92.8 parts, a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1,000. 2 parts, 31.8 parts of a polyoxyethylene glycol monomethyl ether having a hydroxyl value of 101.8 (mgKOH / g), a molecular weight of 550, and 7.7 parts of 1,1,1-trimethylolpropane were added, and nitrogen gas was allowed to flow, followed by stirring. The temperature was raised to 50 ° C. Subsequently, 102.8 parts of isophorone diisocyanate was added, and the reaction was continued at 90 ° C. until NCO%, which is the residual ratio of isocyanate groups, reached 7.5%. A linear urethane prepolymer (A10) obtained by graft polymerization was obtained.
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 37.9 parts of 5-trimethylcyclohexane and 3.8 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 258.3 parts of a linear urethane prepolymer (A6) in which a hydrophilic site is graft-polymerized on the side chain is added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 28, An alcohol solution (X10) of polyurethane polyurea resin having an amine value of 000 and an amine value of 1.2 (mgKOH / g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 11: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Condensate of 3-methyl-1,5-pentanediol and adipic acid having a polyethylene glycol of 92.0 parts, a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1,000. 0 parts, 31.5 parts of a polyoxyethylene glycol monomethyl ether having a hydroxyl value of 101.8 (mgKOH / g), a number average molecular weight (Mn) of 550, and 7.7 parts of 1,1,1-trimethylolpropane were charged. The temperature was raised to 50 ° C. while flowing gas and stirring. Subsequently, 102.0 parts of isophorone diisocyanate was added, and the reaction was continued at 90 ° C. until the NCO%, which is the residual ratio of the isocyanate group, reached 7.5%. A linear urethane prepolymer (A11) obtained by graft polymerization was obtained.
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 37.6 parts of 5-trimethylcyclohexane, 1.9 parts of cyclohexylamine, and 4.3 parts of 3-aminopropyltriethoxysilane were added, and the temperature was raised to 40 ° C. Next, 256.3 parts of a linear urethane prepolymer (A11) in which a hydrophilic site is graft-polymerized on the side chain is added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 26, An alcohol solution (X11) of polyurethane polyurea resin having an amine value of 000 and an amine value of 1.2 (mgKOH / g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Synthesis Example 12: 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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 Condensate of 3-methyl-1,5-pentanediol and adipic acid having a polyethylene glycol of 75.9 parts, a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1,000. 6 parts, 43.5 parts of polyoxyethylene glycol monomethyl ether having a hydroxyl value of 101.8 (mgKOH / g) and a number average molecular weight (Mn) of 550 were charged, and the temperature was raised to 50 ° C. while flowing nitrogen gas and stirring. Subsequently, 55.6 parts of isophorone diisocyanate and 39.9 parts of nurate type polyisocyanate (“Sumidule N3300”, isocyanate equivalent 193.0 manufactured by Sumika Bayer Urethane Co., Ltd.) containing hexamethylene diisocyanate as a main component were added, and an isocyanate group was added. The reaction was carried out at 90 ° C. until the NCO%, which is the residual ratio of A, reached 6.0%, and a linear urethane prepolymer (A12) in which an aliphatic isocyanate group was grafted on both ends and a hydrophilic site was grafted on the side chain was obtained. .
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 30.7 parts of 5-trimethylcyclohexane and 3.8 parts of cyclohexylamine were added, and the temperature was raised to 40 ° C. Next, 265.5 parts of a linear urethane prepolymer (A12) in which a hydrophilic site is graft-polymerized on the side chain is added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 29, An alcohol solution (X12) of polyurethane polyurea resin having an amine value of 000 and an amine value of 1.2 (mgKOH / g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(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 has a hydroxyl value of 112.2 (mgKOH / g) and a number average molecular weight (Mn) of 1 198.7 parts of 1,000,000 polyethylene glycol was charged, and the temperature was raised to 50 ° C. while stirring and flowing nitrogen gas. Subsequently, 75.0 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 4.3%, and both ends were linear urethane prepolymers (B1 )
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 23.9 parts of 5-trimethylcyclohexane and 2.4 parts of di-n-butylamine were added, and the temperature was raised to 40 ° C. Next, 273.7 parts of linear urethane prepolymer (B1) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 43,000, an amine value of 1.2 (mgKOH / An alcohol solution (Y1) of polyurethane polyurea resin of g) was obtained. Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(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 has a hydroxyl value of 280.5 (mgKOH / g) and a number average molecular weight (Mn) of 400. Was charged with 116.9 parts of polypolyethylene glycol, and the temperature was raised to 50 ° C. while stirring under nitrogen gas. Subsequently, 129.8 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 10.0%, and both ends were linear urethane prepolymers (B2 )
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 48.3 parts of 5-trimethylcyclohexane and 5.0 parts of di-n-butylamine were added and the temperature was raised to 40 ° C. Next, 246.7 parts of linear urethane prepolymer (B2) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight (Mw) of 27,000, an amine value of 1.2 (mgKOH / An alcohol solution (Y2) of polyurethane polyurea resin of g) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

(Comparative Synthesis Example 3: 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 has a hydroxyl value of 37.4 (mgKOH / g) and a number average molecular weight (Mn) of 3 24.69 parts of polyethylene glycol having a viscosity of 1,000,000 was charged, and the temperature was raised to 50 ° C. while stirring and flowing nitrogen gas. Subsequently, 36.5 parts of isophorone diisocyanate was added and reacted at 90 ° C. until the NCO%, which is the residual ratio of isocyanate groups, reached 2.4%, and both ends were linear urethane prepolymers (B3 )
Subsequently, 700 parts of 2-propanol, 1-amino-3-aminomethyl-3,5, were added to a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux condenser, and a nitrogen gas introduction tube. 14.2 parts of 5-trimethylcyclohexane and 2.4 parts of di-n-butylamine were added, and the temperature was raised to 40 ° C. Next, 273.7 parts of linear urethane prepolymer (B1) was added and reacted at 40 ° C. for 4 hours to obtain a solid content of 30%, a weight average molecular weight of 41,000, and an amine value of 1.2 (mgKOH / g). An alcohol solution (Y3) of polyurethane polyurea resin (Mw) was obtained.
Subsequently, black ink was prepared by the method described later, and various performances were evaluated.

Examples 1 to 12, Comparative Examples 1 to 3
Using the alcohol solutions X1 to X12 and Y1 to Y3 of the polyurethane polyurea resin, black ink was prepared by the method described later, and various performances were evaluated.

(Black ink adjustment method 1)
A glass bottle is charged with 100 parts of 3.0 mm glass beads, 43 parts of ethanol, 11 parts of MONARCH460 (manufactured by Cabot Specialty Chemicals, Inc.) as carbon black, 1 part of Floren G-700 (manufactured by Kyoeisha Chemical Co., Ltd.), After 40 parts of polyurethane polyurea resin X1 and 5 parts of water were charged, dispersion was performed with a paint conditioner for 1 hour, and then the glass beads were filtered with a wire mesh to obtain black ink XB-1 (Example 1).
Also for Example 2, black ink XB-2 was prepared in the same procedure as in Example 1 with the blending ratio shown in Table 1.

(Black ink adjustment method 2)
A glass bottle is charged with 100 parts of 3.0 mm glass beads, 43 parts of IPA, 11 parts of MONARCH460 (manufactured by Cabot Specialty Chemicals, Inc.) as carbon black, 1 part of Floren G-700 (manufactured by Kyoeisha Chemical Co., Ltd.), After charging 40 parts of polyurethane polyurea resin X3 and 5 parts of water, dispersion was performed with a paint conditioner for 1 hour, and then glass beads were filtered with a wire mesh to obtain black ink XB-3 (Example 3). In Examples 4 to 12 and Comparative Examples 1 to 3, inks were prepared in the same procedure as in Example 3 with the blending ratios shown in Tables 1 and 2.

The following evaluation was performed on the black inks XB1 to XB12 and the black inks YB1 to YB5 obtained above.

(Pigment dispersibility)
The ink described in Table 1, Table 2 and Table 3 was developed with a bar coater # 4 on the treated surface of a biaxially stretched polyethylene terephthalate film (E5102, 12 μm manufactured by Toyobo Co., Ltd.) subjected to corona discharge treatment on one side. The ink ink gloss is visually confirmed. If it is slightly glossy, it is judged as a practical level, but it is desirable that it is more glossy.
(Evaluation)
A: Very glossy. Fluorescent light is reflected ○: Glossy. Fluorescent light is reflected a little.
Δ: Somewhat glossy. Fluorescent light is slightly reflected.
X: There is no gloss. Fluorescent light is hardly reflected.
Xx: There is no gloss. Fluorescent light is not reflected at all.

(Adhesion)
Each black ink listed in Table 1, Table 2, and Table 3 was treated with a bar coater # 4 on the treated surface of a biaxially stretched polyethylene terephthalate film (E5102 12 μm, manufactured by Toyobo Co., Ltd.) having a corona discharge treatment on one side. Colored. After the Nichiban cellophane tape 18 mm width was brought into close contact with the color development surface, the cellophane tape was peeled off vigorously in the vertical direction, and the area ratio of the ink film adhering to the cellophane tape was visually evaluated.
If the area ratio of the ink adhering to the cellophane tape is less than 30%, it can be judged as a practical level, but it is preferable that the ink does not adhere to the cellophane tape.
(Evaluation)
A: Area ratio of ink adhering to cellophane tape 0%
○: Area ratio of ink adhering to cellophane tape is less than 10% Δ: Area ratio of ink adhering to cellophane tape is less than 30% ×: Area ratio of ink adhering to cellophane tape is 30% or more XX: Adhering to cellophane tape More than 80% ink area ratio

(Printability)
Each black ink listed in Table 1, Table 2 and Table 3 was diluted with IPA, and diluted with Zahn Cup No. 3 made by Kogaisha Co., Ltd. so as to be 15 seconds. Using a gravure printing machine equipped with a semi-solid plate, the adjusted ink is printed on the treated surface of a biaxially stretched polypropylene film (Pyrene P-2161 20 μm manufactured by Toyobo Co., Ltd.) that has been subjected to corona discharge treatment on one side. It was. The printing speed is changed to 100 m / min, 150 m / min, and 200 m / min. The ink in the non-image area of the semi-solid plate is not scraped off, and the leaked ink is transferred to the biaxially stretched polypropylene film (plate The degree of occurrence of (fog) was visually evaluated. If the plate fog phenomenon does not occur under the printing conditions of 100 m / min, it can be determined that the level is practical. However, it is desirable that the plate fog phenomenon does not occur even at a higher printing speed.
(Evaluation)
◎: No plate fog phenomenon occurs at a printing speed of 200 m / min. ○: No plate fog phenomenon occurs at a printing speed of 150 m / min. Δ: No plate fog phenomenon occurs at a printing speed of 100 m / min. X: Printing speed of 100 m Plate fog phenomenon occurs at / min. XX: Plate fog phenomenon occurs severely at a printing speed of 100m / min.

(Laminate properties)
Each black ink listed in Table 1, Table 2 and Table 3 was diluted with IPA, and diluted with Zahn Cup No. 3 made by Kogaisha Co., Ltd. so as to be 15 seconds. Print the adjusted ink on the treated surface of a biaxially stretched polyethylene terephthalate film (Emblem ON 15 μm manufactured by Unitika Ltd.) with corona discharge treatment on one side using a gravure printing machine equipped with a solid plate (Helio 175 line). Went. Apply a laminating adhesive with 15 parts of Dick Dry LX-703VL, 1 part of KR-90, and 24.8 parts of ethyl acetate to the ink surface of the printed matter using a bar coater # 8, and use a precision laminator. Then, it is laminated with an L-LDPE film (TUX-HC 60 μm manufactured by Mitsui Chemicals Tosero Co., Ltd.) having a corona discharge treatment on one side.
The laminate is aged at 40 ° C. for 48 hours.
The laminate after aging is three-side sealed with a heat sealer at 180 ° C. for 1 second and 0.1 MPa to make a pouch. Add salad oil / meat sauce / vinegar = 1/1/1 in it. And the upper part is sealed. Using a boil tester, boil treatment was performed at 98 ° C. for 30 minutes, 60 minutes and 90 minutes, and the appearance was visually evaluated.
If the appearance is not abnormal after boiling for 30 minutes, it can be judged as a practical level, but it is desirable to be able to withstand a longer processing time.
(Evaluation)
◎: No abnormality in the appearance even after 90 minutes of boil treatment ○: No abnormality in the appearance after 60 minutes of boil treatment △: No abnormality in the appearance after 30 minutes of boil treatment XX: Lami floating can be confirmed partially XX: Lami Frequent floats or broken bags

The raw materials in the table are as follows.
MONARCH 460 (manufactured by Cabot Specialty Chemicals, Inc.): carbon black, particle size 27 nm, BET specific surface area 84 m ² / g
Florene G-700 (manufactured by Kyoeisha Chemical Co., Ltd.): Carboxy group-containing modified polymer

Claims (13)

1. A printing ink containing a polyurethane polyurea resin, a colorant, and a single type of alcohol solvent, wherein the polyurethane polyurea resin is
   A polyurethane prepolymer (X) obtained by reacting an alcohol component having polyoxyalkylene glycol (A) as an essential component and an isocyanate component having diisocyanate as an essential component; a monoamine (y1) having an alicyclic hydrocarbon group; A printing ink comprising a resin obtained by reacting an amine component (Y) containing diamine (y2) as an essential component.
2. 2. The monoamine (y1) having an alicyclic hydrocarbon group is one or more compounds selected from the group consisting of N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and cyclohexylethylamine. Printing ink.
3. The printing according to claim 1, wherein the diamine (y2) is 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,2-cyclohexanediamine, or dicyclohexylmethane-4,4'-diamine. ink.
4. The printing ink according to claim 1, wherein the polyurethane polyurea resin has a weight average molecular weight (Mw) in the range of 10,000 to 80,000.
5. Furthermore, the printing ink according to claim 1, wherein a monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure is used as the alcohol component together with the polyoxyalkylene glycol (A).
6. The polyurethane prepolymer (X) is obtained by using a monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure in an amount of 5 to 65 parts by mass in 100 parts by mass of the raw material component. Item 5. A printing ink according to item 5.
7. The printing ink according to claim 1, wherein the polyurethane prepolymer (X) is obtained by using a polyester diol (B) together with the polyoxyalkylene glycol (A) as the alcohol component.
8. In the polyurethane prepolymer (X), the polyoxyalkylene glycol (A) and the polyester diol (B) as the alcohol component have a mass ratio [(A) / (B)] of 100/0 to 20/80. The printing ink according to claim 7, wherein the printing ink is obtained using a ratio of
9. The printing ink according to claim 1, wherein a diamine or a monoamine having a trialkoxysilyl group is used in combination as the amine component (Y).
10. A printing ink containing a polyurethane polyurea resin, a colorant, and a single type of alcohol solvent, wherein the polyurethane polyurea resin is
    Reaction of polyester diol (A), monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure, an alcohol component containing a tri- to tetrafunctional polyhydric alcohol (D), and an isocyanate component containing diisocyanate as essential components And a polyurethane prepolymer (X) obtained by reaction, and a resin obtained by reacting an amine component (Y) containing a monoamine (y1) having an alicyclic hydrocarbon group and a diamine (y2). Printing ink.
11. The polyurethane prepolymer (X) comprises, as the alcohol component, polyoxyalkylene glycol (A), monoalcohol (C) having a polyoxyalkylene skeleton in the molecular structure, and tri- to tetrafunctional polyhydric alcohol (D). The printing ink according to claim 10, wherein the printing ink is obtained using the polyester diol (B).
12. The polyurethane prepolymer (X) is obtained by using the tri- to tetrafunctional polyhydric alcohol (D) in a range of 0.1 to 20 parts by mass in 100 parts by mass of the raw material component. The printing ink described.
13. A printed matter printed by using the printing ink according to any one of claims 1 to 12.