JP2016196550A - Alcoholic ink composition, and printed matter and laminated body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink composition which mainly contains isopropanol as a solvent, is excellent in dispersibility and storage stability of a coloring agent, and is excellent in inking property at the time of long-run printing.SOLUTION: There is provided an alcohol printing ink composition which contains a polyurethaneurea resin (D) formed by reaction of polyol (A), diisocyanate (B), and a chain extender (C), a coloring agent (E), a dispersant (F), and a solvent containing isopropanol, where (1) the polyol (A) contains hydrogenated castor oil polyol (A1), (2) the dispersant (F) contains a comb-type dispersant (F1) having a styrene skeleton in the main chain and a polyalkylene oxide chain (f1) in the side chain, and (3) the isopropanol is 50 wt.% or more in the whole solvent.SELECTED DRAWING: None

Description

  The present invention relates to an alcohol-based printing ink composition.

  In recent years, from the strengthening of laws and regulations for each converter and consideration of environmental protection or safety, improvement of the working environment such as non-toluene for printing ink has been promoted. In particular, effective utilization of alcohol with a low environmental load is desired. For example, Patent Document 1 discloses a dispersion of titanium oxide containing ethanol as a main component as a solvent.

  However, in the case of printing inks with alcohol as the main solvent, it is necessary to solubilize the binder resin (that is, to make it hydrophilic). When titanium oxide having a hydrophilic particle surface is used as the pigment, the pigment is a pigment. Although dispersion stability can be maintained, there is a problem that it is difficult to ensure dispersion stability with a hydrophobic organic pigment.

  In addition, when it is difficult to disperse the pigment with the binder resin alone, it is generally possible to use a dispersant or other resin in combination, but such as vinyl chloride-vinyl acetate copolymer that has been widely used in solvent-based inks. Resins are insoluble in alcohol, and many other pigment dispersants are also insoluble in alcohol, and none of them is effective to satisfy pigment dispersibility and printability.

  Thus, for example, Patent Document 2 discloses a method of using an ester solvent in addition to alcohol as a solvent for printing ink. By using an ester solvent in combination, the solubility of the vinyl chloride-vinyl acetate copolymer can be secured, and even organic pigments can be dispersed. For example, ethanol and ethyl acetate are used in combination with solvents with significantly different volatilization rates. In this case, since the ratio of ethanol having a low volatilization rate on the printing plate surface during printing is greatly increased, vinyl chloride-vinyl acetate copolymer is deposited, and there is a problem that printing failure occurs particularly during a long run.

  In particular, among alcohols, ethanol is hydrophilic and therefore has high hygroscopicity. When it is contained as the main solvent of the ink composition, the environmental humidity during printing has a great influence. That is, under high humidity conditions, the solvent composition on the printing plate surface tends to deteriorate the dispersibility of the pigment due to moisture absorption, so that the pigment dispersion state deteriorates or the printability is deteriorated due to insolubilization of the binder resin. On the other hand, isopropanol has a lower hygroscopicity than ethanol, and the proportion of water due to moisture absorption on the printing plate surface under high humidity is 15% by weight or less, so deterioration of the pigment dispersion state and insolubilization of the binder resin can be suppressed. Since the drying rate is equivalent to that of ethanol, it can be suitably used.

  In recent years, from the viewpoint of alcohol-based printing ink, an ink composition comprising 95% by weight or more of a solvent with an alcohol-based solvent (Patent Document 3, Patent Document 4), an ink composition using an alcohol-available polyurethane urea resin having a carbodiimide group From the viewpoint of (Patent Document 5) and further a biomass-based binder resin, printing ink compositions (Patent Document 6 and Patent Document 7) using castor oil polyol or hydrogenated castor oil polyol have been proposed. In particular, in Examples in Patent Document 6 and Patent Document 7, the main solvent is ethanol, and there is a concern about printing defects due to the hygroscopicity.

JP 2002-293860 A JP 2010-144075 A WO2012 / 008339 JP 2013-144732 A Japanese Patent No. 5251122 Japanese Patent No. 5108992 Japanese Patent No. 5273280

  An object of the present invention is to provide a printing ink that is excellent in transferability to a substrate even in a high-temperature and high-humidity environment, and that is excellent in dispersibility and storage stability of a colorant.

  As a result of intensive studies on the above problems, the present inventor has found that the problem can be solved by using the alcohol-based ink composition described below, and has reached the present invention.

The present invention provides a polyurethane urea resin (D) obtained by reacting a polyol (A), a diisocyanate (B), and a chain extender (C),
An alcohol-based printing ink composition comprising a colorant (E), a dispersant (F), and a solvent containing isopropanol, wherein the alcohol is characterized by the following (1), (2) and (3) The present invention relates to a printing ink composition.
(1) The polyol (A) contains hydrogenated castor oil polyol (A1).
(2) The dispersant (F) includes a comb dispersant (F1) having a styrene skeleton in the main chain and a polyalkylene oxide chain (f1) in the side chain.
(3) The said isopropanol is 50 weight% or more in all the solvents.

  The present invention also relates to the above alcohol-based printing ink composition, wherein the polyol (A) further contains a polyether polyol (A2).

  The present invention also relates to the above alcohol-based printing ink composition, wherein the polyol (A) further comprises a polyester polyol (A3) obtained by reacting a dibasic acid (a) with a diol (b). .

  The present invention also relates to the above alcohol-based printing ink composition, wherein the polyalkylene oxide chain (f1) includes a structure having a propylene oxide unit and / or an ethylene oxide unit.

  Moreover, this invention relates to the printed matter formed by apply | coating the said alcohol type printing ink composition to a film base material.

  Moreover, this invention relates to the laminated body formed by laminating | stacking a film on the printing surface of the said printed matter.

According to the present invention, it has been possible to provide a printing ink that is excellent in transferability to a substrate even in a high-temperature and high-humidity environment, and has excellent dispersibility and storage stability of a colorant.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content is not limited.

The alcohol-based printing ink composition of the present invention includes a polyurethane urea resin (D), a colorant (E), a dispersant (F), and a solvent.
The polyurethane urea resin (D) is obtained by reacting the polyol (A), the diisocyanate (B), and the chain extender (C).

  First, the polyol (A) will be described. The polyol (A) of the present invention contains hydrogenated castor oil polyol (A1).

  The hydrogenated castor oil polyol (A1) is not limited to the following examples. For example, castor oil fatty acid (ricinoleic acid) obtained by hydrolyzing castor oil, and castor oil polycondensate by esterification reaction using diol as an initiator ( Castor oil polyol) and then hydrogenating unsaturated groups by a known hydrogenation reaction. It can also be obtained by hydrogenating castor oil fatty acid to form hydrogenated castor oil fatty acid and then esterifying it with diol as an initiator. The diol is not limited to the following examples, but ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6- Hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethyl Pentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether , 2-monoglycerin ether, dimer o , Hydrogenated dimer diol. These hydrogenated castor oil polyols (A1) can be used alone or in admixture of two or more.

  The hydrogenated castor oil polyol (A1) is used for the purpose of imparting pigment dispersibility to the polyurethaneurea resin (D) in a solvent containing 50% by weight or more of isopropanol. The amount of hydrogenated castor oil polyol (A1) used is preferably in the range of 20 to 85% by weight, more preferably in the range of 30 to 75% by weight, out of the total 100% by weight of the polyol (A). If the amount of the hydrogenated castor oil polyol (A1) used is greater than 85% by weight out of the total 100% by weight of the polyol (A), the resolubility may be reduced, and if it is less than 20% by weight, the pigment dispersibility may be reduced. May decrease.

  The molecular weight of the hydrogenated castor oil polyol (A1) is preferably a number average molecular weight of 500 to 10,000, more preferably 1000 to 5,000. If the number average molecular weight is greater than 10,000, the solubility of the polyurethane urea resin (D) in isopropanol may be reduced, and if it is less than 500, the adhesion to the film after printing may be reduced.

  The polyol (A) of the present invention preferably further contains a polyether polyol (A2) from the viewpoint of solubility in isopropanol. The polyether polyol (A2) is not limited to the following examples, but examples thereof include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and copolymerized polyether diols thereof.

  The polyether polyol (A2) is used for the purpose of improving alcohol solubility such as isopropanol of the polyurethane urea resin (D). The amount of the polyether polyol (A2) used is preferably in the range of 15 to 80% by weight, more preferably in the range of 25 to 70% by weight, out of the total 100% by weight of the polyol (A). When the amount of the polyether polyol (A2) used is more than 80% by weight out of the total 100% by weight of the polyol (A), the adhesion to the film substrate may be lowered, and when it is less than 15% by weight, the ink composition The re-solubility of the product may be reduced.

  The molecular weight of the polyether polyol (A2) is preferably a number average molecular weight of 500 to 10000, more preferably 1000 to 5000. When the number average molecular weight is larger than 10,000, the blocking resistance in the printed matter may be lowered, and when it is less than 500, the substrate adhesion in the printed matter may be lowered.

  Furthermore, dibasic acid (a) and diol (b) other than hydrogenated castor oil polyol (A1) and polyether polyol (A2) are used as the polyol (A) of the present invention from the viewpoint of pigment dispersibility or substrate adhesion. The polyester polyol (A3) obtained by reaction can be used in combination.

  The dibasic acid (a) used in the polyester polyol (A3) is not limited to the following examples. For example, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, Examples thereof include dibasic acids such as oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1,4-cyclohexyldicarboxylic acid, dimer acid, and hydrogenated dimer acid. The diol (b) is not limited to the following examples, but ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1 , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3, 5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1- Monoglycerol ether, 2-monoglycerol ether, dimer Ol, hydrogenated dimer diol. Among these, as the polyester polyol (A3), a polymer of adipic acid and 3-methyl-1,5-pentanediol or a polymer of adipic acid and 1,3-propanediol may be used as a pigment dispersion stability or ink obtained. Is particularly preferable in terms of storage stability of the film and transparency in printed matter. The said polyester polyol can be used individually or in mixture of 2 or more types.

  The amount of the polyester polyol (A3) used is preferably in the range of 10 to 50% by weight, more preferably in the range of 20 to 40% by weight, out of the total 100% by weight of the polyol (A). If the amount of the polyester polyol (A3) used is more than 50% by weight out of the total 100% by weight of the polyol (A), the re-dissolvability may be lowered. There is a case.

  The molecular weight of the polyester polyol (A3) is preferably a number average molecular weight of 500 to 10,000, more preferably 1000 to 5,000. If the number average molecular weight is greater than 10,000, the solubility of the polyurethane urea resin (D) in isopropanol may be reduced, and if it is less than 500, the adhesion to the film after printing may be reduced.

The number average molecular weight of the polyol used in the present invention is calculated from the hydroxyl value with the terminal being a hydroxyl group, and is obtained from (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × Hydroxyl valence / Hydroxyl value The hydrogenated castor oil polyol (A1) and polyester polyol (A3) used in the present invention have an acid value of 1.0 mgKOH / g or less is preferable, and 0.5 mgKOH / g or less is more preferable. This is because when the acid value is larger than 1.0 mgKOH / g, the tendency to increase in viscosity of the varnish of the polyurethane urea resin (D) or the printing ink with time increases.

  The polyol (A) can further contain other polyols. Although it is not limited to the following examples, in addition to polymer diols such as polycarbonate diol and polycaprolactone diol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, Diols having no repeating unit such as 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, hydrogenated bisphenol A, dimer diol, hydrogenated dimer diol, etc. Can be mentioned.

  Next, diisocyanate (B) will be described. Although it is not limited to the following examples as diisocyanate (B), Aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, etc. are mentioned. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (also known as MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine Diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diiso Anate, dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tri Examples thereof include diisocyanate, dimerisocyanate obtained by converting a diisocyanate carboxyl group into diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and a dimer acid carboxyl group. These diisocyanate compounds can be used alone or in admixture of two or more. Of these, alicyclic isocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane and isophorone diisocyanate are preferred from the viewpoint of yellowing.

  Next, the chain extender (C) will be described. The chain extender (C) is not limited to the following examples. For example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, dimer acid N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, N- (2-hydroxypropyl) ethylenediamine, N- (2 -Hydroxypropyl) propylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) propylenediamine, N, N'-bis (2-hydroxypropyl) ethylenediamine, N N'-bis (2-hydroxypropyl) propylenediamine and other diamines having a hydroxyl group in the molecule, iminobispropylamine, methyliminobispropylamine, lauryliminobispropylamine and other amines having a plurality of amino groups in the molecule Can also be used. These chain extenders can be used alone or in admixture of two or more.

  Moreover, a monovalent active hydrogen compound can also be used as a polymerization terminator for the purpose of terminating excess reaction. Examples of such compounds include compounds having primary and secondary amino groups, dialkylamines such as di-n-butylamine, amino alcohols, and the like. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. Among these, amino alcohols having primary and secondary amino groups need to be controlled so as to react only with amino groups while avoiding reaction at high temperature when used as a terminal terminator. These end terminators can be used alone or in admixture of two or more.

  When using a polymerization terminator, the chain terminator and chain extender may be used together to carry out the chain extension reaction, and after the chain extension reaction has been performed to some extent with the chain extender, the end terminator is added alone. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

  Next, the form and manufacturing method of a polyurethane urea resin (D) are demonstrated. There is no restriction | limiting in particular about the method of manufacturing a polyurethane urea resin (D), It can manufacture with the manufacturing method of a general polyurethane urea resin. For example, first, polyol (A) and diisocyanate (B) are reacted with a diisocyanate (B) such as ethyl acetate, propyl acetate or t-butanol in a solvent inert to the diisocyanate (B) or without solvent. To make an isocyanate group-containing urethane prepolymer. Subsequently, it can be obtained by reacting an isocyanate group-containing urethane prepolymer with a chain extender (C).

  When the urethane prepolymer is prepared without a solvent, the diisocyanate (B) may be appropriately diluted with a solvent inert to the reaction after completion of the reaction, and diluted with a suitable viscosity to react with the chain extender (C). The viscosity is preferably 100 to 1000 mPa · s, more preferably 200 to 600 mPa · s with a B-type viscometer at 25 ° C. When the viscosity exceeds 1000 mPa · s, the handling property is poor, and when it is less than 100 mPa · s, the reactivity with the chain extender (C) may be deteriorated.

  Furthermore, a catalyst can also be used for this urethanation reaction. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol compound.

  In producing the urethane prepolymer, the ratio of polyol (A) to diisocyanate (B) is the ratio of the number of moles of isocyanate groups in diisocyanate (B) to the number of moles of hydroxyl groups in polyol (A). Is preferably in the range of 1.1 to 3.0, more preferably 1.5 to 2.5. When this ratio is less than 1.1, since the urea group concentration in the obtained polyurethane urea resin is low, the elastic modulus is low and sufficient blocking resistance in the printed matter may not be obtained. On the other hand, if the NCO / OH ratio is greater than 3.0, the urea group concentration is high, so that the solubility is deteriorated and the printability of the ink composition may be deteriorated.

  The polyurethane urea resin (D) preferably has a weight average molecular weight in the range of 10,000 to 100,000. More preferably, it is 15,000-50,000. If it is less than 10,000, the blocking resistance of the printed matter may be lowered, and if it is more than 100,000, the solubility in isopropanol may be lowered to cause printing failure.

  Further, the polyurethane urea resin (D) preferably has an amino group at the terminal and / or main chain. The film substrate on which the ink composition is printed is usually corona-treated in many cases, and a functional group such as a carboxylic acid group or a hydroxyl group exists on the surface of the substrate, and hydrogen bonds with the amino group of the polyurethane urea resin (D). For this reason, the adhesion with the base material is improved, and delamination is difficult after lamination.

  The amount of the amino group is preferably an amine value of 0.5 to 40.0 mg KOH / resin 1 g, and more preferably an amine value of 3.0 to 20.0 mg KOH / resin 1 g. When the amine value is less than 0.5 mg KOH / resin 1 g, the adhesion of the printed matter to the substrate may be reduced, and when it is greater than 40.0 mg KOH / resin 1 g, the ink stability may deteriorate. The polyurethane urea resin (D) is preferably contained in a proportion of 5 to 70% by weight, more preferably 10 to 50% by weight, based on 100% of the total weight of the ink composition.

  Next, the colorant (E) will be described. As the colorant (E), for example, various types used in ordinary inks such as organic pigments, inorganic pigments, and dyes can be used.

  Although the alcohol-based printing ink composition of the present invention uses a solvent containing isopropanol as the main component of the solvent, it has excellent pigment dispersibility not only with inorganic pigments but also with organic pigments.

  Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc. These pigments are mentioned. Further, although not limited to the following examples, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet Quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo Bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, etc. Can be mentioned.

  Examples of inorganic pigments include, but are not limited to, for example, carbon black, aluminum powder, bronze powder, chrome vermillion, chrome lead, cadmium yellow, cadmium red, ultramarine, bitumen, red, yellow iron oxide, iron Examples include black, titanium oxide, and zinc oxide.

  Examples of the dye include, but are not limited to, for example, Tartrazine Lake, Rhodan 6G Lake, Victoria Pure Blue Lake, Alkali Blue G Toner, Brilliant Green Lake, etc. You can also.

  Of these, organic pigments or inorganic pigments are preferably used from the viewpoint of water resistance and heat resistance.

  The colorant (E) is preferably contained in an amount sufficient to ensure the concentration and coloring power of the printing ink, that is, in a proportion of 1 to 50% by weight relative to the total weight of the printing ink, more preferably 5 to 40% by weight. These colorants can be used alone or in combination of two or more.

  Next, the dispersant (F) will be described. In the alcohol-based printing ink composition of the present invention, the dispersing agent (F) contains the comb-shaped dispersing agent (F1) having a polyalkylene oxide (f1) in the side chain, whereby the pigment dispersion stability and the base material during printing are reduced. The transferability is dramatically improved. The comb dispersant (F1) is not particularly limited as long as it is a comb dispersant having a styrene skeleton in the main chain and a polyalkylene oxide chain (f1) in the side chain, and the styrene skeleton has an affinity for pigments, The polyalkylene oxide chain (f1) is responsible for the affinity for isopropanol. Examples of such a compound include a compound obtained by reacting a styrene-maleic anhydride copolymer with a monoamine (G) having a polyalkylene oxide chain, and a polyalkylene oxide skeleton and one radical polymerizable unsaturated group in the molecule. And a copolymer of compound (H) having styrene with styrene.

  Examples of the monoamine (G) having a polyalkylene oxide chain include, but are not limited to, for example, Huntsman's Jeffamine (TM) M600, Huntsman's Jeffamine (TM) M1000, Huntsman's Jeffamine (TM) M2005, Examples include Jeffamine (trademark) M2070 manufactured by Huntsman.

  The compound (H) having a polyalkylene oxide skeleton and one radical polymerizable unsaturated group in the molecule is not limited to the following examples. For example, polyethylene glycol mono (meth) acrylate [hereinafter referred to as “polyethylene glycol monoacrylate” ”And“ polyethylene glycol monomethacrylate ”are collectively referred to as“ polyethylene glycol mono (meth) acrylate ”. ], Polyalkylene glycol mono (meth) acrylates such as polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / polypropylene glycol) mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate ( H1), alkoxy polyalkylene glycol mono (meth) wherein the terminal hydroxyl groups of the above polyalkylene glycol mono (meth) acrylates (H1) such as methoxypolyethylene glycol mono (meth) acrylate are etherified with C1-C4 hydrocarbons In addition to acrylates (H2), monofunctional (meth) acrylic monomers containing one isocyanate group in the molecule such as 2- (meth) acryloyloxyethyl isocyanate, or α, α-dimethyl Examples thereof include a reaction product of a monofunctional vinyl monomer having one isocyanate group in a molecule such as -4-isopropenylbenzyl isocyanate and a monoamine (G) having a polyalkylene oxide chain.

  The structure of the polyalkylene oxide chain (f1) is not particularly limited, but from the viewpoint of pigment dispersibility in a solvent containing isopropanol and compatibility with the polyurethane urea resin (D), a propylene oxide unit, an ethylene oxide unit, It preferably contains a trimethylene oxide unit, a tetramethylene oxide unit, and an arbitrary combination unit thereof. Further, the terminal group of the polyalkylene oxide chain (f1) is not particularly limited, but it preferably has a hydroxyl group or an ether bond with a hydrocarbon group having 1 to 10 carbon atoms.

More preferably, the structure of the polyalkylene oxide chain (f1) includes a structure containing a propylene oxide unit and / or an ethylene oxide unit represented by the following general formula (1). A mixture of seeds or more can be used.
General formula (1)
_{- (C 3 H 6 O)} n - (C 2 H 4 O) m -R
(In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n and m are each an integer of 0 to 50, provided that the total of n and m is 9 to 50.)

  The ratio of styrene to the polyalkylene oxide chain (f1) in the comb-shaped dispersant (F1) is such that the styrene unit and the polyalkylene oxide chain (G) unit are used from the viewpoint of pigment dispersibility in alcohol and solubility in alcohol. The molar ratio is preferably 2: 1 to 10: 1. When the ratio of styrene units is larger than 10: 1, the solubility of the dispersant (F) in isopropanol may be poor, and when the ratio of styrene units is smaller than 2: 1, the pigment dispersibility is poor. It may become.

  The comb-shaped dispersant (F1) is a molecule that forms a polar functional group such as an amino group, a carboxyl group, or a hydroxyl group as needed for the purpose of improving the compatibility with the polyurethane urea resin (D) and improving the dispersion stability. It can be introduced and used inside. Further, when the comb-shaped dispersant (F1) has an amino group in the molecule, it can be chlorinated with a monofunctional carboxylic acid, and when it has a carboxyl group in the molecule, it can be chlorinated with a monofunctional amine or metal ion. it can. In the case of using the comb-shaped dispersant (F1), from the viewpoints of compatibility with the polyurethane urea resin (D), dispersion stability, and blocking resistance of the printed matter, the amount of the ink composition is 0.1% relative to the total weight of the ink composition of 100% by weight. It is preferably contained in a proportion of 1 to 20% by weight, more preferably 0.5 to 10% by weight.

  In order to stably disperse the colorant (E) in a solvent containing isopropanol, the dispersant (F) can be further used in combination with a known dispersant. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. Although not limited to the following, the dispersant (F) is 0.05% by weight or more with respect to 100% by weight of the total amount of ink from the viewpoint of pigment dispersion stability of the ink, and 15% by weight or less from the viewpoint of suitability for lamination. And preferably contained in the ink. Furthermore, it is more preferable that it is contained in the range of 0.1 to 10% by weight.

  The alcohol-based printing ink composition of the present invention contains 50% by weight or more of isopropanol in a total of 100% by weight of the solvent. Examples of other solvents include, but are not limited to, for example, aliphatic alcohols having 1 to 7 carbon atoms such as methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, and tertiary butanol. , Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, ketones such as acetone and methyl ethyl ketone, ethyl acetate and propyl acetate, etc. Examples thereof include esters and carbonates such as dimethyl carbonate.

  The alcohol-based printing ink composition of the present invention can contain water as a solvent for the purpose of improving the dispersion stability of the pigment. The amount of water that may be contained is preferably in the range of 0.5 wt% to 20.0 wt% in a total of 100 wt% of the solvent. If the amount of water in the solvent is larger than 20.0% by weight, the drying speed of the solvent becomes slow, and it may not be sufficiently dried in the drying process at the time of printing, and water or the solvent may remain in the coating film. When the amount of water in the solvent is less than 0.5% by weight, the temporal stability of the ink composition may be lowered.

  In the alcohol-based printing ink composition of the present invention, in addition to the polyurethane urea resin (D), a resin soluble in a solvent containing isopropanol may be used in combination. For example, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, alkyl-modified cellulose resin, nitrocellulose resin, cellulose-modified resin, acrylic resin , Polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and modified resins thereof The content thereof is preferably 0.5% by weight to 20% by weight with respect to 100 parts by weight of the ink composition.

  In the alcohol-based printing ink composition of the present invention, known additives may be appropriately mixed and used as necessary. For example, pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, silica components, wax components and the like can be used.

  The alcohol-based printing ink composition of the present invention is prepared by premixing a polyurethane urea resin (D), a solvent, a colorant (E), and a dispersant (F), and performing a pigment dispersion treatment using a disperser such as a sand mill. It can be obtained by doing.

  The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. 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.

  In the case where bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

  The viscosity of the ink produced by the above method is about 8.0 to 30 sec in viscosity from Zahn Cup # 4 from the viewpoint of preventing the pigment from settling and dispersing appropriately, from the viewpoint of workability efficiency during ink production and printing. It is preferably in the range of 10 sec to 15 sec.

  The viscosity of the ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, resin, colorant, organic solvent, and the like. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.

  The alcohol-based printing ink composition 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 printed matter of the present invention comprises the printing ink composition of the present invention, a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, polycarbonate or polylactic acid, a polystyrene resin such as polystyrene, AS resin or ABS resin, nylon, polyamide, Apply to the film or sheet substrate made of polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or a composite material of these using the above printing method, and fix the film by drying in an oven. It can be obtained.

  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 normal extrusion lamination (extrusion laminating) method of laminating molten resin via various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium on the printed surface of this printed matter, and urethane on the printed surface The laminate of the present invention can be obtained by a known laminating process such as a dry laminating method in which an adhesive such as is applied and a plastic film is laminated, or a direct laminating method in which a melted polypropylene is directly pressed and laminated on a printing surface.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise noted. The hydroxyl value is calculated by converting the amount of hydroxyl group in 1 g of resin calculated by esterifying or acetylating the hydroxyl group in the resin with excess acid anhydride and back titrating the remaining acid with alkali to the number of mg of potassium hydroxide. The value obtained in accordance with JIS K0070. The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and the measurement method was performed according to JIS K0070 (1996). The method for measuring the amine value was as described below. The molecular weight (weight average molecular weight) of the polyurethane resin was obtained as a polystyrene equivalent molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (measuring solvent: tetrahydrofuran). The method for measuring the amine value is as follows.

[Method for measuring amine value]
Weigh 0.5-2 g of sample accurately. (Sample amount: Sg) 30 mL of neutral ethanol (BDG neutral) is added to a precisely weighed sample and dissolved. The obtained solution is titrated with a 0.2 mol / l ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine value was determined by the following (Formula 1) using the titration amount (AmL) at this time.
(Formula 1) Amine number = (A × f × 0.2 × 56.108) / S

(Synthesis Example 1) <Preparation of polyurethane urea resin (PU1)>
In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, hydrogenated castor oil polyol (product name: “URIC PH-100”, manufactured by Ito Oil Co., Ltd., hydroxyl value 41.6 mg KOH / g, number average molecular weight 2700) ) 91.4 parts, 91.7 parts of polypropylene glycol (hydroxyl value 56.1 mgKOH / g, number average molecular weight 2000), 7.1 parts of 1,3-propanediol, and 77.3 parts of isophorone diisocyanate. Then, a urethane prepolymer was produced by reacting at 100 ° C. for 6 hours under a nitrogen stream. Next, 66.9 parts of ethyl acetate was added to the obtained urethane prepolymer to obtain a uniform solution of the urethane prepolymer. Next, the urethane prepolymer solution was dropped into a mixture composed of 32.5 parts of isophoronediamine and 633 parts of isopropanol over 1 hour, and then reacted for 1 hour to obtain a polyurethane urea resin (PU1) solution. The resulting polyurethane urea resin (PU1) solution has a resin solid content concentration of 30% by weight and a viscosity of 250 mPa · s (25 ° C.). The amine value of the resin solid content is 6.1 mg KOH / g of resin, and the weight average molecular weight is 35,000. Met.

(Synthesis Examples 2 to 9) <Preparation of polyurethane urea resins (PU2 to PU9)>
Castor oil polyol (product name: “URIC HF-2009” manufactured by Ito Oil Co., Ltd., hydroxyl value 41.8 mgKOH / g, number average molecular weight 2700) and (product name: “URIC H1824” manufactured by Ito Oil Co., Ltd., hydroxyl value 71.2 mgKOH / g, number average molecular weight 1576), number average molecular weight 2000 polyester diol “PMPA2000” obtained from adipic acid and 3-methyl-1,5-pentadiol, number average obtained from adipic acid and 1,2-propanediol Polyester diol “PPA2000” having a molecular weight of 2000 and polytrimethylene glycol “PTG2000” having a number average molecular weight of 2000 are prepared, and using the raw materials shown in Table 1, polyurethane urea resin solutions PU2 to PU9 are prepared in the same manner as in Synthesis Example 1. Obtained. In Table 1, “PPG2000” represents polypropylene glycol having a number average molecular weight of 2000, “PDO” represents 1,3-propanediol, “IPDI” represents isophorone diisocyanate, and “IPDA” represents isophoronediamine. In addition, the number average molecular weight of the polyol excluding PDO used in the present invention was calculated by assuming that the polymer was all diol molecules from the hydroxyl value.

  A summary of Synthesis Examples 1-9 is summarized in Table 1.

(Synthesis Example 10) <Preparation of Comb Dispersant (DP1)>
In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, polyalkylene oxide monoamine (product name: “Jeffamine M2005” manufactured by Huntsman, number average molecular weight 1953, solid content 100%, in the general formula (1) 163 parts of n = 29, m = 6, R = CH3), and a styrene-maleic anhydride copolymer (product name: “SMAEF60” manufactured by SARTOMER, acid value: 156 mg KOH / g, solid content: 100%, styrene: anhydrous maleic acid 60 parts of acid ratio = 6: 1) were charged and reacted at 150 ° C. for 8 hours under a nitrogen stream, and then 334 parts of isopropanol was added to obtain a uniform solution of comb dispersant (DP1). The obtained comb dispersant (DP1) solution had a resin solid content concentration of 40% by weight, an acid value of resin solid content of 9.0 mgKOH / resin 1 g, an amine value of 0.1 mgKOH / resin 1 g, and a weight average molecular weight. Was 30000.

Synthesis Example 11 <Preparation of Comb Dispersant (DP2)>
In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, polyalkylene oxide monoamine (product name: “Jeffamine M1000” manufactured by Huntsman, number average molecular weight 1000, solid content 100%, in the general formula (1) n = 3, m = 19, R = CH3) 83.4 parts, and styrene-maleic anhydride copolymer (product name: “SMAEF60” manufactured by SARTOMER, acid value 156 mg KOH / g, solid content 100%, styrene: 60 parts of maleic anhydride ratio = 6: 1) were charged and reacted at 150 ° C. for 8 hours under a nitrogen stream, and then 215 parts of isopropanol was added to obtain a uniform solution of comb dispersant (DP2). The obtained comb dispersant (DP2) solution had a resin solid content concentration of 40% by weight, an acid value of the resin solid content of 10.0 mgKOH / resin 1 g, an amine value of 0.1 mgKOH / resin 1 g, and a weight average molecular weight. Was 30000.

Synthesis Example 12 <Preparation of Comb Dispersant (DP3)>
In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, polyalkylene oxide monoamine (product name: “Jeffamine M2005”, manufactured by Huntsman, number average molecular weight 1953, solid content 100%, general formula (1) N = 29, m = 6, R = CH3) was charged in 93.3 parts, and 6.7 parts of 2-isocyanatoethyl acrylate was added dropwise over 1 hour from a dropping tank at 40 ° C. under a nitrogen stream. Reaction was performed at 40 ° C. for 2 hours to obtain a reaction product (DP3-1). Further, 50 parts of isopropanol, 30 parts of styrene, and 1.1 parts of acrylic acid were added and uniformly mixed by stirring. To this, 4.0 parts of dimethyl 2,2′-azobis (2-methylpropionate) and 50 parts of IPA were evenly mixed. The mixed solution was added dropwise over 30 minutes and then reacted at 80 ° C. for 8 hours, and then 103 parts of isopropanol was further added to obtain a uniform solution of a comb-shaped dispersant (DP3). The obtained comb dispersant (DP3) solution had a solid content of 40% by weight, an acid value of 9.0 mgKOH / resin 1 g, an amine value of 0.1 mgKOH / resin 1 g, and a weight average molecular weight of 30000.

(Production Examples 1 to 28)
<Production Example 1: Preparation of ink composition J-1>
40 parts of polyurethane urea resin (PU1), 5 parts of comb-shaped dispersant (DP1), C.I. 10 parts of I Pigment Blue 15: 3, 5 parts of water, and 10 parts of isopropanol were mixed and kneaded for 30 minutes with a sand mill (media: 0.8 mm glass beads), then 40 parts of isopropanol were added and mixed. Thus, an ink composition was obtained.
<Production Examples 2-28: Preparation of ink compositions (J-2 to J-14) and (K-1 to K-14)>
Alcohol ink compositions (J-2 to J-14) and (in the same manner as in Production Example 1 except that the materials and compositions (parts by weight or blending ratio) described in Table 2-1 and Table 2-2 were used. K-1 to K-14) were adjusted.

(Examples 1-12 and Comparative Examples 1-12)
<Creation of printed matter>
The ink composition (K-4 to K-6) is ethanol, and the ink compositions (J-1 to J-14) and (K-1 to K-3, K-7 to K-14). ) Is diluted with isopropanol so that the viscosity becomes 15 seconds (25 ° C., Zaan Cup No. 3), and the engraving 175 line, the plate type Elon gate, and the gradation plate having a plate depth of 100% to a plate depth of 5% are provided. Printed on a corona-treated surface of a 20 μm thick corona-treated biaxially oriented polypropylene (OPP) film “Pyrene P2161” (manufactured by Toyobo Co., Ltd.) at a printing speed of 100 m / min. It was. The printing was performed in an environment with an air temperature of 27 ° C., a humidity of 55% (W1 to W14) and (Y1 to Y14), an air temperature of 30 ° C., and a humidity of 65% (X1 to X14) and (Z1 to Z14).

<Evaluation of ink composition and printed matter>
The following tests were performed on the ink composition and the obtained printed matter. The results are shown in Table 3-1 and Table 3-2. In the following tests, the practical level is evaluated as ○ to ○ △.

(1) Color development The ink compositions (J-1 to J-14) and (K-1 to K-14) immediately after preparation were coated on a polypropylene film with a bar coater (Miyabar No. 6), and color was visually observed. The property (gloss) was evaluated.
○: The coated surface is dark and glossy.
○ △: The color of the coated surface is dark but the gloss is slightly inferior.
(Triangle | delta): The color of the coating surface is a little thin, but gloss is a little inferior.
Δ ×: The coating surface is slightly thin and has no gloss.
X: The coated surface is thin and dull.

(2) High-temperature storage stability of ink composition The ink compositions (J-1 to J-14) and (K-1 to K-14) immediately after preparation were stored at 50 ° C for 1 week, and the viscosity before and after the test was measured. Based on the rate of change, the following evaluation criteria were used. Viscosity was measured using the Zahn cup no. 4 (25 ° C.).
○: Change rate of viscosity is less than 3 seconds.
○ Δ: Viscosity change rate is less than 5 seconds.
Δ: Viscosity change rate is 5 seconds or more and less than 10 seconds.
Δ ×: Viscosity change rate is 20 seconds or more.
X: The rate of change in viscosity is 60 seconds or more.

(3) Plate depth 10% inking (temperature 27 ° C-humidity 55%)
The thickness (transferability) of the ink was evaluated using a printing portion of the printed matter (W1 to W14) and (Y1 to Y14) having a printing depth of 10% after 4000 m printing. The evaluation was judged from the coloring ratio of the ink in the printed image area.
○: The meat is 100%.
○ △: The meat is 90% or more.
(Triangle | delta): Meat is 60 to 90%.
Δx: 30% to 60%.
X: The flesh is 30% or less.

(4) Plate depth 5% part wearability (temperature 27 ℃-humidity 55%)
The thickness (transferability) of the ink was evaluated using a printing portion of the printed matter (W1 to W14) and (Y1 to Y14) having a printing depth of 5% after 4000 m printing. The evaluation was judged from the coloring ratio of the ink in the printed image area.
○: The meat is 100%.
○ △: Inking is 80% or more.
(Triangle | delta): Meat is 50 to 80%.
Δ ×: Inking is 20 to 50%.
X: The flesh is 20% or less.

(5) Plate depth 10% part wearability (temperature 30 ° C-humidity 65%)
The ink set-up property (transferability) was evaluated using a printed part (X1 to X14) and (Z1 to Z14) having a printing depth of 10% after 4000 m printing. The evaluation was judged from the coloring ratio of the ink in the printed image area.
○: The meat is 100%.
○ △: The meat is 90% or more.
(Triangle | delta): Meat is 60 to 90%.
Δx: 30% to 60%.
X: The flesh is 30% or less.

(6) Plate depth 5% part inking (temperature 30 ° C-humidity 65%)
The ink set-up property (transferability) was evaluated using a printed part (X1 to X14) and (Z1 to Z14) having a printing depth of 5% after 4000 m printing. The evaluation was judged from the coloring ratio of the ink in the printed image area.
○: The meat is 100%.
○ △: Inking is 80% or more.
(Triangle | delta): Meat is 50 to 80%.
Δ ×: Inking is 20 to 50%.
X: The flesh is 20% or less.

  From the evaluation results, polyurethane urea resin (D) obtained by reacting polyol (A), diisocyanate (B), and chain extender (C), colorant (E), dispersant (F), and solvent An alcohol-based printing ink composition containing isopropanol, wherein the polyol (A) contains hydrogenated castor oil polyol (A1), the dispersant (F) has a styrene skeleton in the main chain, and a polyalkylene in the side chain The alcohol-based printing ink composition containing the comb-type dispersant (F1) having an oxide chain (f1) and having the isopropanol content of 50% by weight or more in the total solvent is excellent in pigment dispersion stability and inking property during long run printing. It was found to be a printing ink composition.

Claims (6)

Polyurethane urea resin (D) obtained by reacting polyol (A), diisocyanate (B), and chain extender (C);
An alcohol-based printing ink composition comprising a colorant (E), a dispersant (F), and a solvent containing isopropanol, wherein the alcohol is characterized by the following (1), (2) and (3) Printing ink composition.
(1) The polyol (A) contains hydrogenated castor oil polyol (A1).
(2) The dispersant (F) includes a comb dispersant (F1) having a styrene skeleton in the main chain and a polyalkylene oxide chain (f1) in the side chain.
(3) The said isopropanol is 50 weight% or more in all the solvents. The alcohol-based printing ink composition according to claim 1, wherein the polyol (A) further contains a polyether polyol (A2). The alcohol-based printing ink composition according to claim 1 or 2, wherein the polyol (A) further comprises a polyester polyol (A3) obtained by reacting the dibasic acid (a) with the diol (b). . The alcohol-based printing ink composition according to any one of claims 1 to 3, wherein the polyalkylene oxide chain (f1) includes a structure having a propylene oxide unit and / or an ethylene oxide unit. The printed matter formed by apply | coating the alcohol type printing ink composition in any one of Claims 1-4 to a film base material. The laminated body formed by laminating | stacking a film on the printing surface of the printed matter of Claim 5.