JP6256103B2 - Printing ink composition - Google Patents

Description

  The present invention relates to a printing ink composition, and more particularly to a printing ink composition having excellent laminating properties for various plastic films.

Gravure printing and flexographic printing are used for soft packaging materials used in foods and daily necessities to add beauty and functionality. In order to cope with the high performance of these flexible packaging materials, a post-processing called laminating is generally performed. For this reason, printing inks are required to have a high degree of lamination suitability, boil retort suitability, and the like.

  Studies on the suitability for laminating and suitability for boiling and retort have been extensively conducted. For example, as disclosed in JP-A-2002-69353 and JP-A-2013-213109, various binder resins for printing ink, The printing ink used has been developed.

In general, the laminate strength, which is an index of laminating suitability, requires time to converge to a certain strength after laminating, but in recent years, the work process has become more efficient and the interval between the ink printing process and the laminating process has increased. In addition, the interval between the laminating process and the bag making process is shorter than before. Therefore, high laminate strength is required immediately after the laminating process, that is, the rising speed of the laminate strength is required. However, in the above literature, the laminate strength immediately after processing is not always satisfactory.

JP 2002-69353 A JP 2013-213109 A

  An object of the present invention is to provide a printing ink composition, which has a high lamination strength immediately after laminating with respect to various plastic films, that is, has a quick rise in lamination strength.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a printing ink composition containing dimer diol exhibits a high laminate strength immediately after laminating, leading to the present invention.

That is, the present invention
Binder resin containing 0.1% by weight or more and 5% by weight or less of dimer diol (a), polyurethane resin (b), and rosin (c-1) and / or rosin derivative having an acid value of 120 mgKOH / g or more The present invention relates to a printing ink composition comprising (c-2) in an amount of 0.2% by weight to 3% by weight and an organic solvent.

Furthermore, the present invention provides
The weight average molecular weight of a polyurethane resin (b) is 10,000-100000, It is related with the said printing ink composition characterized by the above-mentioned .

Furthermore, the present invention provides
Furthermore, it is related with the printing ink composition characterized by containing isocyanate type hardening | curing agent (d).

Furthermore, the present invention provides
The present invention relates to a printed matter obtained by printing a printing ink composition on a plastic film using a gravure printing machine.

Furthermore, the present invention provides
The present invention relates to a laminate obtained by laminating a printed material and a base material via a laminating adhesive.

  According to the present invention, it is possible to provide a printing ink composition having a high lamination strength immediately after lamination.

  Hereinafter, the printing ink composition of the present invention will be described.

The printing ink composition of the present invention contains dimer diol (a). Dimer diol (a) is a reduction reaction product of a polymer fatty acid. Polymeric fatty acids are also called dimer acids, and the presence of C18 unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, dry oil fatty acids or semidry oil fatty acids, and lower monoalcohol esters of these fatty acids as catalysts. Alternatively, it is a non-existing bimolecular polymer (dimer). Commercially available products include Sobamol 650NS and Sobamol 908 manufactured by BASF Japan, Prepol 2030 and Prepole 2033 manufactured by Croda Japan, and PESPOL HP-1000 manufactured by Toa Gosei.

Since the dimer diol (a) contains a hydrophobic carbon chain and a hydrophilic hydroxyl group, by containing the dimer diol in the printing ink, the film and ink (especially the binder resin in the printing ink composition) It is thought that it contributes to the adhesion effect, and the rise of the laminate strength is accelerated.

In the present invention, the dimer diol (a) is preferably contained in the printing ink composition in an amount of 0.1% by weight or more from the viewpoint of laminate strength and 5% by weight or less from the viewpoint of suitability for boil and retort.

In the present invention, the dimer diol (a) is used by directly adding it to the printing ink composition. By adding the dimer diol (a), the rise of the laminate strength is improved. In addition, when the dimer diol (a) is added to the printing ink composition, it may be added before the dispersion or after the dispersion, but it is more preferable to add it after the dispersion.

In the present invention, examples of the binder resin used in the printing ink composition include resins used in general inks, paints, and recording agents. Examples of the binder resin include polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, nitrocellulose resin, acrylic resin, polyester resin, Alkyd resin, polyvinyl chloride resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin and the like can be mentioned. The resins can be used alone or in admixture of two or more. The resin content (in terms of solid content) is preferably 4 to 25% by weight, more preferably 6 to 20% by weight, based on the total weight of the ink.

Among the above resins, the polyurethane resin (b) is preferable. The polyurethane resin (b) is widely used as a resin for laminating ink.

The polyurethane resin (b) in the present invention is obtained by reacting a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol and a diisocyanate compound with an organic diamine. That is, in the synthesis method of the polyurethane resin (b), first, a polyol and a diisocyanate compound are used as a prepolymer reaction, and if necessary, a solvent inert to an isocyanate group is used. A urethane prepolymer having an isocyanate group at the terminal is produced by reacting at a temperature of ° C, and then the urethane prepolymer and the organic diamine are reacted at 10 to 80 ° C as a chain extension reaction. The end points of the prepolymer reaction and chain extension reaction are determined by viscosity measurement, NCO peak by IR measurement, amine value measurement by titration, and the like.

In the present invention, the polyurethane resin (b) is preferably a polyurethane resin having an amine value. The amine value of the polyurethane resin (b) is preferably 2.0 to 13.0 mg KOH / g, and the laminate strength is improved within this range.

In the present invention, the molar ratio [NCO] / [OH] between the isocyanate group of the diisocyanate compound and the hydroxyl group of the polyol in the prepolymer reaction of the polyurethane resin (b) is preferably 1.5 to 2.8. When [NCO] / [OH] is in the range of 1.5 to 2.8, the effect of improving the rise of the laminate strength by the dimer diol (a) is exhibited. On the other hand, when [NCO] / [OH] is less than 1.5, the polyurethane resin film is too soft and the blocking resistance tends to be inferior. Further, when [NCO] / [OH] is 2.8 or more, the film of the polyurethane resin becomes too hard, and even when the dimer diol (a) is added, the rising speed of the laminate strength by the dimer diol (a) is increased. It is difficult to obtain an improvement effect.

The weight average molecular weight of the polyurethane resin (b) in the present invention is preferably 10,000 to 100,000. More preferably, it is 20000-60000. When the weight average molecular weight is in the range of 10,000 to 100,000, the rising speed of the laminate strength and the blocking resistance tend to be improved.

  As the polyol used in the polyurethane resin (b) in the present invention, various known polyester polyols, polyether polyols, polycaprolactones, and the like can be used, and one or more of them may be used in combination. Examples of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3propanediol, 1, 3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, Saturated or unsaturated such as diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol Low molecular weight poly And adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, trimellitic acid Polyester polyols obtained by dehydrating condensation or polymerization of polyvalent carboxylic acids such as pyromellitic acid or their anhydrides, cyclic ester compounds such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) And polyester polyols obtained by ring-opening polymerization of lactones such as Examples of polyether polyols include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran. It is preferable to use a polyester polyol and a polyether polyol in combination.

As the diisocyanate compound used in the polyurethane resin (b) in the present invention, various known diisocyanates of aromatic, aliphatic or alicyclic can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 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, 2,4,4- Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate Isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and carboxyl groups of dimer acid were converted to isocyanate groups. Dimer isocyanate is a typical example. These can be used alone or in admixture of two or more. Isophorone diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferred.

Examples of the organic diamine used in the polyurethane resin (b) in the present invention include ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, and dicyclohexylmethane-4,4'-diamine. Also, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrrole Amines having a hydroxyl group in the molecule, such as pyrethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine, can also be used. These organic diamines can be used alone or in admixture of two or more, and isophorone diamine is preferred. Furthermore, diethylenetriamine, iminobispropylamine: (IBPA, 3,3′-diaminodipropylamine), N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6-iminodihexylamine Polyfunctional amines having 3 or more amino groups such as 3,7-diazanonan-1,9-diamine and N, N′-bis (3-aminopropyl) ethylenediamine can be used in combination with the organic diamine.

  The organic solvent used for the polyurethane resin (b) in the present invention includes a mixed solvent of an ester solvent and an alcohol solvent. Examples of ester solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and alcohol solvents include methanol, ethanol, n-propanol, isopropanol, It is preferable to use a known solvent such as an alcohol solvent such as n-butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether.

A catalyst can also be used for the prepolymer 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.

A reaction terminator may be used for the chain extension reaction. Examples of the reaction terminator include dialkylamines such as di-n-butylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino. Amines having a hydroxyl group such as 2-ethyl-1,3-propanediol can also be used. Furthermore, monoamine type amino acids such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, sulfamic acid and the like can also be mentioned.

Furthermore, it is preferable to use rosin (c-1) and / or rosin derivative (c-2) from the viewpoint of adhesiveness.

Examples of rosin (c-1) in the present invention include gum rosin, tall oil rosin, and wood rosin. In general, rosin is an amber, amorphous resin obtained from pine and is a mixture because it is obtained from nature.Abietic acid, neoabietic acid, parasritric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, You may isolate and use for every component called dehydroabietic acid, and these are also defined as rosin in this invention.

The rosin derivative (c-2) in the present invention is a compound obtained by modifying the above rosin, and is specifically listed below.
(1) Hydrogenated rosin: A rosin in which weather resistance is improved by adding hydrogen (hydrogenation) to a conjugated double bond.
(2) Disproportionated rosin: Disproportionation means that two molecules of rosin react with each other and two molecules of abietic acid with conjugated double bonds are converted to aromatic one and the other is a single double bond. It is a modification that becomes a molecule. In general, the weather resistance is inferior to that of hydrogenated rosin, but it is improved compared to untreated.
(3) Rosin-modified phenolic resin: In ink for offset printing, rosin-modified phenolic resin is often used as a main binder. The rosin-modified phenol resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, and has been used as a tackifier for tackiness and adhesives (tackfire) for a long time.
(5) Rosin-modified maleic acid resin: A resin obtained by addition reaction of maleic anhydride to rosin and, if necessary, a hydroxyl group-containing compound such as glycerin esterified with a hydroxyl group and grafted.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosins and rosin derivatives can also be used, and these can be used not only alone but also in combination.

Furthermore, the acid value of rosin (c-1) and rosin derivative (c-2) in the present invention is preferably 120 mgKOH / g or more. When the acid value is 120 mgKOH / g or more, the initial rise of the laminate strength is further improved. More preferably, the acid value is 160 mgKOH / g or more. Further, the solid content in the rosin (c-1) and / or rosin derivative (c-2) in the printing ink composition is 0.2% by weight or more from the viewpoint of laminate strength, and 3% by weight from the viewpoint of suitability for boil and retort. % Or less is preferable.

The printing ink composition of the present invention is manufactured by dispersing a colorant in an organic solvent with a binder resin or the like using a dispersing machine, and mixing the obtained pigment dispersion with a binder resin, various additives, an organic solvent, or 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 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. In the present invention, the present invention can also be applied to a medium containing no colorant.

In order to stably disperse a colorant such as a pigment, the binder resin alone can be dispersed. However, in order to disperse the pigment stably, a pigment dispersant can be used in combination. As the pigment dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. The pigment dispersant is preferably contained in an amount of 0.05% by weight or more with respect to the total weight of the printing ink composition from the viewpoint of ink stability and 10% by weight or less from the viewpoint of suitability for lamination. Furthermore, it is more preferable that it is contained in the range of 0.1 to 3% by weight.

In the printing ink composition of the present invention, an inorganic colorant and an organic colorant can be used as the colorant. Examples of the inorganic colorant include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, aluminum hydroxide, chromium oxide, silica, carbon black, aluminum, mica (mica), and the like. From the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance, titanium oxide is preferable for the white colorant, and titanium oxide having a basic pigment surface is more preferable. Aluminum is in the form of powder or paste, but is preferably used in the form of paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and concentration. Barium sulfate, calcium carbonate, and aluminum hydroxide are called extender pigments and are used as extenders to improve fluidity, strength, and optical properties. On the other hand, examples of the organic colorant include organic pigments and dyes used in general inks, paints, and recording agents. Examples thereof include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline. Indigo ink is copper phthalocyanine, and transparent yellow ink is C.I. I. Pigment No Yellow 83 is preferably used.

The colorant is preferably contained in an amount sufficient to ensure the density and coloring power of the printing ink, that is, in a proportion of 1 to 50% by weight with respect to the total weight of the printing ink. These colorants can be used alone or in combination of two or more.

In addition, additives such as leveling agents, antifoaming agents, waxes, silane coupling agents, plasticizers, light stabilizers, infrared absorbers, ultraviolet absorbers, fragrances, and flame retardants may be included as necessary. .

As the organic solvent used in the printing ink composition of the present invention, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene are used in the same manner as the organic solvent used in the polyurethane resin. Known solvents such as ester solvents such as glycol monomethyl ether acetate, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether and propylene glycol monomethyl ether can be used. In recent years, there has been a demand to eliminate aromatic organic solvents such as toluene and xylene and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone from the viewpoint of the working environment. In the printing ink composition of the present invention, a solvent that eliminates this is preferred. Used.

When bubbles or unexpectedly large particles are included in the printing ink composition, 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 printing ink composition is preferably in the range of 10 mPa · s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa · s or less from the viewpoint of workability efficiency during ink production and printing. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.

In the present invention, it may be used as a one-component printing ink composition, or an isocyanate-based curing agent (d) may be added and used as a two-component printing ink composition. As the isocyanate curing agent (d), for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), respectively, adduct type polyisocyanate (adduct body), biuret type polyisocyanate (biuret body), respectively. , Isocyanurate type polyisocyanate (isocyanurate form) and the like, for example, an adduct obtained from the reaction of 1 mol of trimethylolpropane and 3 mol of HDI, a biuret obtained from the reaction of 1 mol of water and 3 mol of HDI, Examples include isocyanurate bodies obtained from cyclic trimerization reaction of HDI. When used as a two-component printing ink, the addition amount of the polyisocyanate curing agent is preferably 0.5 to 5% by weight based on the ink.

The printing ink composition in the present invention can be used in known printing methods such as gravure printing and flexographic printing. Gravure printing is preferable. In gravure printing, it is diluted with a diluting solvent to a viscosity and concentration suitable for printing, and supplied to each printing unit alone or mixed.

As a substrate to which the printing ink composition of the present invention can be applied, polyolefin such as polyethylene or polypropylene, polyethylene terephthalate, polyester such as polycarbonate or polylactic acid, polystyrene resin such as polystyrene, AS resin or ABS resin, nylon, polyamide, There are various films of polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum foil, etc., or a film or sheet made of a composite material thereof. These substrates may be subjected to vapor deposition coating treatment and / or coating treatment such as polyvinyl alcohol on the surface of a metal oxide, for example, GL- manufactured by Toppan Printing Co., Ltd. in which aluminum oxide is vapor deposited on the substrate surface. Examples include AE and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd. Further, those treated with additives such as an antistatic agent and an ultraviolet ray inhibitor, and those obtained by subjecting the surface of the substrate to corona treatment or low temperature plasma treatment can be used as necessary.

The printed matter in the present invention is obtained by applying the printing ink composition using the printing method described above, and drying and fixing by oven drying. The drying temperature is usually about 40 to 60 ° C.

The laminate in the present invention can be obtained by applying at least one layer of lamination to a printed matter obtained by printing the printing ink composition. There are various processing methods for laminating, but typical examples include (1) extrusion laminating method, (2) dry laminating method and the like.

(1) The extrusion laminating method is a method in which a thermoplastic resin is melted on the printing surface of the obtained printed matter and extruded from a slit-like die called a T die into a film shape and laminated on a substrate. is there. In many cases, an anchor coating agent is applied in advance to the printed surface of a printed material and then laminated. It is also possible to extrude the molten resin onto the printed surface of the printed material and bond the sealant from another unwinder. As the anchor coating agent, an imine-based, butadiene-based, or isocyanate-based anchor coating agent can be used. Specific examples include EL-420 (imine type), EL-452 (butadiene type), EL-530A / B (isocyanate type), EL-540 / CAT-RT32 (isocyanate type), manufactured by Toyo Morton. It is done. As the molten resin, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used. Specific examples include Novatec LD LC600A (low density polyethylene) manufactured by Nippon Polyethylene. Examples of the sealant include the above-mentioned various films, cellophane, paper, aluminum foil and the like used for the substrate, or a film or sheet made of a composite material thereof. Specific examples include TUX-FCD (LLDPE) manufactured by Mitsui Chemicals, Inc., Cello Co., Ltd., FCMN (CPP) manufactured by Phutamura Chemical Co., Ltd., and Diastar (VMPET) manufactured by Reiko.

(2) The dry laminating method is a method in which an adhesive is diluted to an appropriate viscosity with an organic solvent, applied to the printed surface of the obtained printed matter, dried and then pressure-bonded with a sealant for lamination. As the adhesive, a two-component type of polyol / isocyanate is mainly used. Specifically, TM-250HV / CAT-RT86L-60, TM-550 / CAT-RT37, TM-314 / CAT-14B manufactured by Toyo Morton Co., Ltd. Etc. Examples of the sealant include the above-mentioned various films, cellophane, paper, aluminum foil and the like used for the substrate, or a film or sheet made of a composite material thereof. Specifically, there are TUX-FCD (LLDPE) manufactured by Mitsui Chemicals Tosero Co., Ltd., ZK93KM (CPP) manufactured by Toray Industries, Inc., Dialeraster (VMPET) manufactured by Reiko, 2203 (VMPP) manufactured by Toray Industries, Inc., and the like.

The laminate obtained by the above method becomes a packaging bag by heat-sealing the sealant surfaces. Therefore, a film for imparting heat sealability is used for the sealant that hits the innermost side in the packaging bag. For example, polyolefin such as unstretched polyethylene or polypropylene can be used.

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 was acetylated with an excess of an acetylating reagent and the amount of hydroxyl group in 1 g of resin calculated by back titrating the remaining acid with alkali was converted to mg of potassium hydroxide. The value is a value obtained according to 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 molecular weight was determined as a polystyrene-converted molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus. Tetrahydrofuran was used as a measurement solvent for GPC. Moreover, the measuring method of an 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 value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

[Synthesis of polyurethane resin]
[Synthesis Example 1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, a poly (3-methyl-1,5-pentaneadipate) diol having a molecular weight of 2000 (PMPA2000: hydroxyl value 56.1 mgKOH / g) 160.41 parts, poly (1,2-propylene glycol) having a molecular weight of 2000 (PPG2000: hydroxyl value 56.1 mgKOH / g) 68.75 parts, isophorone diisocyanate 50.93 parts, tin 2-ethylhexanoate (II) 0 0.03 part and 82.50 parts of ethyl acetate were charged and reacted at 90 ° C. for 3 hours under a nitrogen stream to obtain 362.62 parts of a solution of a terminal isocyanate prepolymer. Then, 18.54 parts of isophoronediamine, 1.07 part of 2-hydroxyethylethylenediamine, 0.30 part of di-n-butylamine, 327.50 parts of ethyl acetate and 289.97 parts of isopropyl alcohol were obtained. A solution of a terminal isocyanate prepolymer was gradually added at room temperature, and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin (PU01) having a solid content of 30.0%, a weight average molecular weight of 40000, and an amine value of 6.0 mgKOH / g. Obtained.

[Synthesis Example 2]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, a poly (3-methyl-1,5-pentaneadipate) diol having a molecular weight of 2000 (PMPA2000: hydroxyl value 56.1 mgKOH / g) 160.87 parts, poly (1,2-propylene glycol) having a molecular weight of 2000 (PPG2000: hydroxyl value 56.1 mgKOH / g) 68.95 parts, isophorone diisocyanate 51.08 parts, tin 2-ethylhexanoate (II) 0 0.03 parts and 82.50 parts of ethyl acetate were charged and reacted at 90 ° C. for 3 hours under a nitrogen stream to obtain 363.43 parts of a solution of a terminal isocyanate prepolymer. Subsequently, 17.79 parts of isophoronediamine, 1.03 part of 2-hydroxyethylethylenediamine, 0.28 part of di-n-butylamine, 327.50 parts of ethyl acetate and 289.97 parts of isopropyl alcohol were obtained. A solution of a terminal isocyanate prepolymer was gradually added at room temperature, and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin (PU02) having a solid content of 30.0%, a weight average molecular weight of 85,000, and an amine value of 1.5 mgKOH / g. Obtained.

[Preparation of resin solution of vinyl chloride vinyl acetate copolymer]
30 parts of Solvine AL manufactured by Nissin Chemical Industry Co., Ltd. was dissolved in 70 parts of ethyl acetate to obtain a resin solution (V1) of a vinyl chloride vinyl acetate copolymer having a solid content of 30%.

[Preparation of rosin solution]
Each rosin or rosin derivative was dissolved in 80 parts of ethyl acetate to obtain a rosin solution (R1 to R3) having a solid content of 20.0%. The acid value of each rosin or rosin derivative is as follows.
R1: Harrier Star MSR-4
(Harima Kasei Co., Ltd., rosin derivative) Acid value 120-150 mgKOH / g
R2: Pine Crystal KR-612
(Arakawa Chemical Industries, Rosin) Acid value 165-175mgKOH / g
R3: Harimac AS-5
(Harima Kasei Co., Ltd., rosin derivative) Acid value 185-210 mg KOH / g

[Preparation of white printing ink composition]
In this specification, Examples 1-8 and 12-14 are reference examples.
[Example 1]
35.0 parts of Titanic JR-805 (manufactured by Teica, titanium oxide), 10.0 parts of polyurethane resin (PU01), 5.0 parts of n-propyl acetate and 5.0 parts of isopropyl alcohol were stirred and mixed in a sand mill. After meat, 30.0 parts of polyurethane resin (PU01), 8.1 parts of ethyl acetate, 5.4 parts of isopropyl alcohol, and 1.5 parts of Sobamol 650NS (BASF Japan, dimer diol) are mixed by stirring and printed in white. An ink composition (W01) was obtained. To 100 parts of the obtained white printing ink composition, 50 parts of an n-propyl acetate: isopropyl alcohol mixed solvent (mass ratio 75:25) was added and mixed as a diluent solvent to obtain a diluted ink.

[Examples 2 to 7] [Comparative Example 1]
The white printing ink composition (W02-7 and W14) was obtained by the same operation as Example 1 by the preparation ratio described in Table 1. Sobamol 650NS and Sobamol 908 in Table 1 are dimer diols manufactured by BASF Japan, and Pripol 2033 is dimer diols manufactured by Croda Japan. However, in Comparative Example 1, no dimer diol is added. A diluted ink was also obtained by the same operation as in Example 1.

[Example 8]
3. 35.0 parts of Titanic JR-805 (manufactured by Teica, titanium oxide), 10.0 parts of polyurethane resin (PU01), 1.5 parts of Sobamol 908 (manufactured by BASF Japan, dimer diol), n-propyl acetate After stirring and mixing 0 parts, 5.0 parts of isopropyl alcohol and kneading with a sand mill, 30.0 parts of polyurethane resin (PU01), 8.1 parts of ethyl acetate, and 5.4 parts of isopropyl alcohol were stirred and mixed. An ink composition (W08) was obtained. Further, diluted ink was obtained by the same operation as in Example 1.

[Example 9]
30.0 parts of Titanic JR-805 (manufactured by Teica, titanium oxide), 10.0 parts of polyurethane resin (PU01), 5.0 parts of n-propyl acetate, and 5.0 parts of isopropyl alcohol were stirred and mixed in a sand mill. After meat, 30.0 parts of polyurethane resin (PU01), 5.1 parts of ethyl acetate, 3.4 parts of isopropyl alcohol, 1.5 parts of Sobamol 908 (manufactured by BASF Japan, dimer diol), 5 rosin solution (R1) 0.0 part was stirred and mixed to obtain a white printing ink composition (W09). Further, diluted ink was obtained by the same operation as in Example 1.

[Examples 10 to 11]
The white printing ink composition (W10-11) was obtained by the same operation as Example 9 by the preparation ratio described in Table 1. A diluted ink was also obtained by the same operation as in Example 1.

[Example 12]
30.0 parts of Titanic JR-805 (manufactured by Teica, titanium oxide), 10.0 parts of polyurethane resin (PU01), 5.0 parts of n-propyl acetate, and 5.0 parts of isopropyl alcohol were stirred and mixed in a sand mill. After meat, 30.0 parts of polyurethane resin (PU01), 1.5 parts of Sobamol 908 (manufactured by BASF Japan, dimer diol), 8.1 parts of ethyl acetate, 5.4 parts of isopropyl alcohol were stirred and mixed, and LP 3.0 parts of a super curing agent (manufactured by Toyo Ink Co., Ltd., isocyanate curing agent) was added to obtain a white printing ink composition (W12). To 103 parts of the obtained white printing ink composition, 50 parts of an n-propyl acetate: isopropyl alcohol mixed solvent (mass ratio 75:25) was added and mixed as a diluent solvent to obtain a diluted ink.

[Example 13] [Comparative Example 2]
A white printing ink composition (W13 and W15) was obtained by the same operation as in Example 12 at the charging ratio shown in Table 1. However, in Comparative Example 2, no dimer diol is added. A diluted ink was also obtained by the same operation as in Example 12.

[Preparation of indigo printing ink]
[Example 14]
LIONOL BLUE FG-7330 (CI Pigment Blue 15: 3) (Toyocolor) 10.0 parts, polyurethane resin (PU01) 15.0 parts, n-propyl acetate 5.0 parts, isopropyl alcohol 5.0 After stirring and mixing parts with a sand mill, 20.0 parts of polyurethane resin (PU01), 1.5 parts of Sobamol 908 (BASF Japan, dimer diol), 26.1 parts of ethyl acetate, 17.4 isopropyl alcohol Parts were stirred and mixed to obtain an indigo printing ink composition (C01). 50 parts of n-propyl acetate: isopropyl alcohol mixed solvent (mass ratio 75:25) was added to and mixed with 100 parts of the indigo printing ink composition to obtain a diluted ink.

[Comparative Example 3]
In the same manner as in Example 14, the indigo printing ink composition (C02) was obtained at the charging ratio shown in Table 1. However, no dimer diol is added. A diluted ink was also obtained in the same manner as in Example 14.

  The diluted ink was applied to a corona-treated OPP film (Futamura Chemical Co., Ltd. FOR # 20) and a corona-treated nylon film (Unitika Ltd. ON-RT # 15) with a gravure proofing machine equipped with a 35 μm gravure printing plate at a speed of 40 m. / Min and printed at 40-50 ° C. to obtain a printed matter. The following tests were performed using the obtained printed matter.

[Lamination strength]
An imine anchor coat agent (EL420, manufactured by Toyo Morton Co., Ltd.) is applied to the printed matter of the above OPP film with an NV 1 wt% methanol solution, and melted polyethylene at a line speed of 100 m / min using an extrusion laminator (manufactured by Musashinokikai). (Manufactured by Nippon Polyethylene Co., Ltd., LC600A) was melted at 320 ° C., laminated at 18 μm, and laminated with VMPET (manufactured by Reiko Co., Ltd., Diastar H27 # 12). Furthermore, CPP (manufactured by Futamura Chemical Co., Ltd., FCMN # 20) was similarly laminated thereon. The laminating process is performed within 3 hours after the printing process. After the laminating step, the laminate was cut into a length of 150 mm and a width of 15 mm, opened at the ink-film interface, and the laminate strength in the 90 ° direction was measured using a Tensilon tensile tester. The measurement is performed 3 hours and 1 day after the laminating process. The determination criteria were as follows.
A: 1.5 N / 15 mm or more ○: 1.0 N / 15 mm or more and less than 1.5 N / 15 mm Δ: 0.5 N / 15 mm or more and less than 1.0 N / 15 mm (more than this is a practical level)
×: Less than 0.5 N / 15 mm [Boil suitability]
Isocyanate-based anchor coating agent (EL530A and B manufactured by Toyo Morton Co., Ltd.) is applied to the above nylon film printed matter, and melted polyethylene (Nippon Polyethylene Co., Ltd.) at a line speed of 100 m / min using an extrusion laminator (manufactured by Musashinokikai). (LC600A) was melted at 320 ° C. and laminated at 18 μm, and aging was performed at LLDPE (manufactured by Mitsui Chemicals, Inc., TUX-FCD # 40) at 40 ° C. for 48 hours. Thereafter, the LLDPE surface is heat sealed to make a bag, and the resulting bag is filled with soup of vinegar: salad oil: tomato ketchup = 1: 1: 1 (weight ratio) as a content, 85 ° C. 30 The presence / absence of litter float after performing the boil treatment for minutes was visually determined by appearance. The determination criteria were as follows.
○: No abnormality △: Blister occurred in some areas (more than this is a practical level)
×: Delamination occurred

The evaluation results are summarized in Table 1. The printing ink compositions of Examples 1 to 14 have a better laminate strength than Comparative Examples 1 to 3, and in particular, when containing dimer diol, the laminate strength measured after 3 hours of lamination is even better. there were.

Claims (5)

Binder resin containing 0.1% by weight or more and 5% by weight or less of dimer diol (a), polyurethane resin (b), and rosin (c-1) and / or rosin derivative having an acid value of 120 mgKOH / g or more A printing ink composition comprising (c-2) in an amount of 0.2 wt% to 3 wt% and an organic solvent. The printing ink composition according to claim 1, wherein the weight average molecular weight of the polyurethane resin (b) is 10,000 to 100,000. Furthermore, according to claim 1 or 2 printing ink composition according to, characterized in that an isocyanate-based curing agent (d). The printed matter formed by printing the printing ink composition in any one of Claims 1-3 on a plastic film using a gravure printing machine. A laminate obtained by laminating the printed matter according to claim 4 and a base material via a laminating adhesive.