JP2013213111A - Printing ink composition for gravure rotary printing for paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink composition that has excellent adhesiveness to a paper base having high hydrophobicity such as acid-proof paper, etc., and in which, after printing, a polyethylene layer can be extrusion laminated to a printing surface without an adhesive in a printing ink composition using a vinyl chloride-vinyl acetate copolymer and an acrylic resin.SOLUTION: A printing ink composition for gravure rotary printing for paper includes a vinyl chloride-vinyl acetate copolymer and an acrylic resin as binder resins and 1-40 wt.% of glycerol based on the total solid content of ink.

Description

  The present invention relates to a printing ink composition for paper gravure rotation. More specifically, a printing ink composition for gravure rotation for paper, which can be laminated even when printed on a highly hydrophobic paper substrate such as acid-resistant paper, and has good ink stability, and a printed matter of the printing ink composition And a laminated product using the same.

  Nitriated cotton, urethane resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, and the like are used in printing ink compositions for paper gravure rotation used in paper containers for food applications. A printing ink composition for gravure printing for paper containers prepared using these may be subjected to post-processing such as coating OP varnish after printing or laminating polyethylene resin or the like.

  Non-coated paper, coated paper, polyethylene laminated paper, etc. are mentioned as paper base materials used for these paper containers, but especially for acidic contents such as yogurt cups, in order to prevent deterioration of the base paper due to the contents, Uses acid-resistant paper that is hard to soak up water and has strong paper strength, and is laminated to prevent deterioration of the paper container due to the contents.

  As a printing ink composition for gravure rotation for paper for laminating, the suitability of laminating cotton, a metal chelate compound, a printing ink containing a plastic component, and coated paper has been reported. However, sizing agents with strong hydrophobicity are added to acid-resistant paper to prevent water soaking, and printing on solvent-resistant gravure printing ink on acid-resistant paper resulted in strong oleophilicity of the sizing agent. The ink soaks into the base paper and causes chalking, which causes a problem of poor laminate strength during lamination.

JP 2000-319568 A

  An object of the present invention is to provide a printing gravure printing ink composition for paper that has excellent laminate strength even when printed on a paper base material by preventing permeation into strongly hydrophobic base paper such as acid-resistant paper.

  As a result of intensive investigations to achieve the above-mentioned goals, the inventors of the present invention are excellent in laminated products by using a binder resin composed of vinyl chloride-vinyl acetate copolymer (A) and acrylic resin (B). Also when laminating strength is given and 1-40% by weight of glycerin as an additive is added to the total solid content of the ink to prevent permeation into strongly hydrophobic base paper, and when printing on strongly hydrophobic base paper The present invention was completed by finding a printing ink composition for paper gravure rotation having excellent laminate strength as a laminate.

That is, the present invention is a gravure rotary printing ink composition comprising a binder resin comprising a vinyl chloride-vinyl acetate copolymer (A) and an acrylic resin (B), glycerin, a colorant and a solvent,
The present invention relates to a printing ink composition for paper gravure rotation, characterized in that glycerin is contained in an amount of 1 to 40% by weight based on the total solid weight of the ink.

  Furthermore, the present invention relates to the above-described printing ink composition for gravure rotation for paper, wherein the acrylic resin (B) has an acid value of 50 to 250 KOH mg / g and a weight average molecular weight of 5000 to 20000. .

In the present invention, when the solid content weight of the vinyl chloride-vinyl acetate copolymer (A) is W1, and the solid content weight of the acrylic resin (B) is W2,
Solid weight ratio W1 / W2 = 99 / 5-20 / 80 It is related with the above-mentioned printing ink composition for gravure rotation for paper.

  Further, according to the present invention, when the binder resin further includes a polyester-based urethane resin (C) and the solid content weight is W3, the total solid content weight of the binder resin is W / W3 = 95/5. The present invention relates to the above-mentioned printing ink composition for gravure rotation for paper, which is 50/50.

  Moreover, this invention relates to the printed matter formed by printing on the paper base material said paper gravure rotary ink composition.

  Furthermore, the present invention relates to a laminated product obtained by oxidizing the above-mentioned printed matter and directly laminating a polyethylene resin without using an adhesive.

  The present invention uses a binder resin composed of a vinyl chloride-vinyl acetate copolymer (A) and an acrylic resin (B) and adds glycerin as an additive to provide an excellent laminate even when printed on a highly hydrophobic base paper. It was possible to obtain a printing ink composition for paper gravure printing having strength.

  The vinyl chloride-vinyl acetate copolymer (A) used in the printing ink composition for paper gravure rotation according to the present invention comprises vinyl chloride monomer, vinyl acetate monomer, vinyl alcohol and 2-hydroxyethyl acrylate, 2-hydroxyethyl. It can be obtained by copolymerizing a monomer having a hydroxyl group such as methacrylate or 2-hydroxypropyl acrylate or a monomer having a carboxyl group such as maleic acid at an appropriate ratio. In particular, a vinyl chloride-vinyl acetate copolymer (A) having a hydroxyl group that does not require an aromatic solvent such as toluene for dissolution is preferred from the viewpoint of the working environment. Specific examples of the vinyl chloride-vinyl acetate copolymer (A) include sorbine A (manufactured by Nissin Chemical Co., Ltd.) and VAGH (manufactured by Dow Chemical Co., Ltd.).

  The acrylic resin (B) used in the printing gravure printing ink composition for paper of the present invention can be produced by a conventionally known method, and the production method is not particularly limited. The acrylic resin (B) can be obtained by polymerizing a monomer having a carbon-carbon unsaturated double bond in one molecule in a solvent using a polymerization initiator. Here, the monomer having a carbon-carbon unsaturated double bond in one molecule is (i) acrylic acid and its derivatives, (ii) aromatic vinyl monomer, (iiii) olefin-based carbonization Examples include hydrogen monomers, (iv) vinyl ester monomers, (v) vinyl halide monomers, (vi) vinyl ether monomers.

(I) Examples of acrylic acid derivatives include (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl ( Examples thereof include alkyl (meth) acrylates such as (meth) acrylate.
(Ii) Examples of the aromatic vinyl monomer include styrenes in which a part of hydrogen such as styrene, methylstyrene, ethylstyrene, chlorostyrene, monofluoromethylstyrene is substituted with fluorine.
(Iiii) Examples of olefinic hydrocarbon monomers include ethylene, propylene, butadiene, isobutylene, isoprene and the like. (Iv) Examples of vinyl ester monomers include vinyl acetate.
(V) Examples of vinyl halide monomers include vinyl chloride and vinylidene chloride.
(Vi) vinyl methyl ether etc. are mentioned as an example of a vinyl ether monomer.

  Moreover, the monomer which has a carbon-carbon unsaturated double bond in 1 molecule can use the monomer which has a crosslinkable functional group. Examples of the monomer having a functional group include (vii) a monomer having a hydroxyl group, (viii) a monomer having an isocyano group, and (ix) a monomer having an epoxy group.

  (Vii) Examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Polyethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and the like.

  (Viii) Examples of monomers having an isocyano group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) Examples thereof include those obtained by reacting a hydroxyalkyl (meth) acrylate such as acrylate with a polyisocyanate such as isophorone diisocyanate.

  (Ix) Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, and the like.

  Depending on the required performance, a monomer having a carbon-carbon unsaturated double bond in one molecule can be used alone, or a mixture of two or more can be used as preferred monomers. Examples include styrene, methyl (meth) acrylate, butyl (meth) acrylate, acrylic acid, and (meth) acrylic acid.

  The acrylic resin (B) can be obtained by using the above monomer in the presence or absence of a solvent and using a polymerization initiator. Examples of the polymerization initiator include ordinary peroxides or azo compounds such as benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl. Peroctoate, etc. are used. As the solvent, ethyl acetate, isopropanol, ethanol, methyl ethyl ketone, or the like is used.

  The acid value of the acrylic resin (B) is preferably 50 to 250 KOH mg / g. If the acid value is less than 50 KOH mg / g, poor laminate strength may occur. If the acid value exceeds 250 KOH mg / g, the compatibility with the vinyl chloride-vinyl acetate copolymer (A) decreases, causing separation and ink. Ink stability may decrease, such as an increase in viscosity. Moreover, the weight average molecular weight 5000-20000 is preferable. If it is less than 5000, the film is brittle and the blocking resistance of the printed matter may be reduced. If it exceeds 20000, the compatibility with the vinyl chloride-vinyl acetate copolymer (A) is reduced, and the ink stability is lowered. There is a case.

  The colorant used in the present invention includes organic pigments and inorganic pigments, but dyes can also be used in addition to pigments. Specific examples of organic pigments include 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 Examples thereof include red, industron blue, pyrimidine yellow, thioindiobordeaux, thioindigo magenta, aniline black, and daylight fluorescent pigment. Specific examples of the inorganic pigment include carbon black, aluminum powder, bronze powder, chrome vermillion, chrome lead, ultramarine, cyanide, bengara, yellow iron oxide, iron black, titanium oxide, and zinc oxide. Specific examples of the dye include tartrazine lake, rhodarin 6G lake, Victoria pure blue lake, alkali blue G toner, brilliant green lake and the like, and other coal tars can also be used. The colorants can be used alone or in admixture of two or more for the purpose of adjusting the hue and density. The colorant is used in an amount that ensures the concentration and coloring power of the ink composition, preferably 4 to 50% by weight based on the total weight of the ink composition. Even without a colorant, the same laminate strength and ink stability can be obtained.

  The present invention also requires additives such as a leveling agent, an antifoaming agent, a wax, a plasticizer, an infrared absorber, an ultraviolet absorber, a flame retardant, and a pigment dispersant when used in combination with an extender pigment. Can be used according to.

  The solvent used for the preparation of the acrylic resin varnish of the present invention is preferably a hydrocarbon-based, ketone-based or alcohol-based non-aromatic system. Specifically, hydrocarbons such as methylcyclohexane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, npropyl acetate, and butyl acetate, methanol, ethanol, and propanol Alcohol organic solvents such as ruthenium, isopropanol and butanol can be used alone or in admixture of two or more.

  As the glycerin used in the present invention, a commercially available pharmacopoeia product is used. Specifically, pharmacopoeia glycerin (manufactured by Shin Nippon Rika Co., Ltd.) is mentioned.

  The glycerin used in the present invention needs to be contained in an amount of 1 to 40% by weight based on the total solid content of the ink. If it is less than 1% by weight, the penetration into a strongly hydrophobic paper substrate such as acid-resistant paper cannot be suppressed, resulting in poor laminate strength. When it is 40% by weight or more, the drying of the film is delayed, and the blocking resistance is lowered.

  When the solid content weight of the vinyl chloride-vinyl acetate copolymer (A) used in the present invention is W1, and the solid content weight of the acrylic resin (B) is W2, the solid content weight ratio W1 / W2 = 95/5 It is desirable to be 20/80. If the vinyl chloride-vinyl acetate copolymer (A) increases beyond W1 / W2 = 95/5, the laminate strength may be weakened. If the acrylic resin (B) exceeds 20/80, the pigment dispersibility increases. In some cases, the ink stability decreases due to a decrease in the amount of ink and precipitation.

  Further, in the present invention, in addition to the binder resin, the polyester urethane resin (C) has a solid content weight of W3, and the W / W3 is 95/5 to 50 to the total solid content weight W of the binder resin. By including / 50, the laminate strength can be further improved. When W3 is smaller than W / W3 = 95/5, a sufficient effect of improving the laminate strength is not observed. When W3 exceeds W / W3 = 50/50, the blocking resistance of the printed matter may be lowered.

  The polyester-based urethane resin (C) used in the present invention is a urethane-modified polyol obtained by reacting a polyol with a polyisocyanate and a chain extender using one or more commonly used polyols that are generally used. If necessary, the polyisocyanate is reacted at a temperature of 10 to 150 ° C. using an inert solvent for the isocyanate group and, if necessary, a urethanization catalyst to produce a prepolymer having an isocyanate group at the terminal. Then, this prepolymer is reacted with a chain extender and a terminal terminator to obtain a polyurethane polyol resin, or an organic polyol compound, a polyisocyanate compound and a chain extender are reacted in one step to obtain a polyurethane polyol resin. Manufactured by known methods such as one-shot Rukoto can be.

  Examples of the polyol include polyether polyols of polymers or copolymers such as methylene oxide, ethylene oxide, and tetrahydrofuran, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propanediol. 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, 1,4-butylenediol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol Or unsaturated polyols are mentioned.

  In addition, one or more of these polyols and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, speric acid, azelaic acid, sebacin Obtained by ring-opening polymerization of lactones such as polyester polyols obtained by dehydration condensation or polymerization of polycarboxylic acids such as acids, or anhydrides thereof, or cyclic ester compounds such as polycaprolactone and polyvalerolactone. Polyester polyols such as polycarbonate polyols obtained by reaction with dimethyl carbonate, ethylene carbonate, etc.

  Among these, in order to ensure the laminate strength improving effect and the compatibility with the acrylic resin (B), it is preferable to use a polyester polyol, and it is preferable to account for 50% by weight or more of the polyol.

  As the isocyanate used in the urethane-modified polyol, various known isocyanates that are generally used in the production of polyurethane resins can be used. Examples thereof include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), and alicyclic diisocyanates such as isophorone diisocyanate (IPDI). These diisocyanate compounds can be used alone or in admixture of two or more.

  The chain extender used for the urethane-modified polyol includes ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and the like, as well as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine and the like in the molecule. Amines having a hydroxyl group can also be used. These chain extenders can be used alone or in admixture of two or more.

  A monovalent active hydrogen compound can also be used as a terminal terminator for the purpose of terminating the reaction. Examples of such compounds include compounds having primary and secondary amino groups, dialkylamines such as di-n-butylamine, amino alcohols having a hydroxyl group, and alcohols such as ethanol and isopropyl alcohol. These end terminators can be used alone or in admixture of two or more. Here, when an amino group is used as a chain extender, it reacts with an isocyanate group to form a urea bond, so that the resulting resin is a polyurethane / urea resin. In the present invention, these resins are also polyurethane resins. To do.

  Furthermore, a catalyst can also be used for preparation of the polyester-type urethane resin varnish (C) used for this invention. Examples of the catalyst that can be used include a tertiary amine catalyst such as triethylamine and a metal catalyst such as tin. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol compound.

  Moreover, it is preferable from the surface of reaction control to use a solvent for preparation of the polyester-type urethane resin varnish (C) used for this invention. As the solvent that can be used, those that dissolve the polyurethane adhesive composition are preferable, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as dioxane, tetrahydrofuran, ethyl acetate, npropyl acetate, butyl acetate. And esters. These may be used alone or in combination as a mixed solvent.

  The printing ink composition for paper gravure rotation of the present invention can be used by printing on a strongly hydrophobic paper substrate such as acid-resistant paper by a gravure printing method, and also includes non-coated paper, coated paper, polyethylene laminated paper, etc. Similarly, it can be printed on a paper substrate by a gravure printing method. The printing ink composition for paper gravure printing of the present invention is diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing at the time of printing, and is supplied alone or mixed to each printing unit.

  The printed matter printed with the printing ink composition for paper gravure rotation according to the present invention is subjected to an acid value treatment such as corona treatment, and then a polyethylene resin is extruded onto the printed surface without an adhesive, followed by laminating. Can be obtained. It is also possible to use an adhesive, and the same laminating process is performed by the usual extrusion laminating method in which polyethylene resin is laminated on the printing surface through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium. You can also get things. The laminating method is not limited to the above-mentioned extrusion laminating method. The laminating method of the present invention is applied by a known laminating process such as a dry laminating method in which an adhesive such as urethane is applied to the printing surface and a plastic film is laminated. A workpiece can also be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the present invention, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Preparation of vinyl chloride-vinyl acetate copolymer varnish a1>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 25 parts of vinyl chloride-vinyl acetate copolymer A1 (Solvine A Nissin Chemical Co., Ltd.) and 75 parts of ethyl acetate were added. The mixture was dissolved in a nitrogen stream at 60 ° C. for 2 hours to obtain a vinyl chloride-vinyl acetate copolymer varnish a1 having a solid content of 25%.

<Preparation of vinyl chloride-vinyl acetate copolymer varnish a2>
Using a vinyl chloride-vinyl acetate copolymer varnish A2 (VAGH Dow Chemical Co., Ltd.), a vinyl chloride-vinyl acetate copolymer varnish a2 was prepared in the same manner as the vinyl chloride-vinyl acetate copolymer varnish a1. Solid content 25%.

<Synthesis of acrylic resin varnish b1>
<Synthesis Example 1>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 10 parts of methacrylic acid, 30 parts of methyl (meth) acrylate, 20 parts of butyl (meth) acrylate, 40 parts of styrene and 200 of methyl ethyl ketone In a nitrogen stream, the temperature was raised to 90 ° C. while stirring, 2 parts of azobisisobutyronitrile was added, the polymerization reaction was carried out for 2 hours, 50 parts separated and purified were mixed with 34 parts of ethyl acetate. And 16 parts of isopropyl alcohol were added to obtain an acrylic resin varnish b1 having a solid content of 50%, an acid value of 50 KOH mg / g, and a weight average molecular weight of 5000.

<Synthesis of acrylic resin varnish b2 to b6>
<Synthesis Examples 2-6>
Prepared in the same manner as the acrylic resin varnish b1 at the monomer blending ratio in Table 1, and prepared acrylic resin varnishes b2 to b6. The type and amount of the organic solvent used are the same as in Example 1.

<Preparation of polyester urethane resin varnish c1>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, a polyester diol having a number average molecular weight of 2000 (hereinafter referred to as PMPA2000) obtained from adipic acid and 3-methyl-1,5-pentanediol. 32.394 parts, polypropylene glycol having a number average molecular weight of 2000 (hereinafter referred to as PPG 2000) 16.173 parts, isophorone diisocyanate 8.635 parts, stannous 2-ethylhexylate 0.010 parts and npropyl acetate 10. 0 parts was charged and reacted at 85 ° C. for 3 hours under a nitrogen stream, and then 10.0 parts of npropyl acetate was added and cooled to obtain 72.212 parts of a solution of a terminal isocyanate prepolymer. Subsequently, 2.233 parts of isophoronediamine, 0.565 parts of di-n-butylamine, 78.000 parts of npropyl acetate and 42.000 parts of isopropyl alcohol were mixed with a solvent solution of the obtained terminal isocyanate prepolymer. 212 parts are gradually added at room temperature, and then reacted at 50 ° C. for 1 hour. Polyester polyurethane having a solid content of 30%, a solvent composition of npropyl acetate / isopropyl alcohol = 50/50 (weight ratio), and a weight average molecular weight of 55,000 A resin varnish c1 was obtained.

[Example 1]
<Preparation of printing ink composition 1 for gravure printing for paper>
Vinyl chloride-vinyl acetate copolymer varnish a 1: 38 parts, acrylic resin varnish b 1: 1 part, indigo pigment (“Fastgen Blue FGF-SD” manufactured by DIC Corporation): 10 parts, mixed solvent (n-propyl acetate / Ethyl acetate / isopropyl alcohol = 25/25/50 (weight ratio)): 50.8 parts, glycerin: 0.2 parts were kneaded with an Eiger mill to prepare a printing ink composition 1 for indigo paper gravure rotation. did.
Subsequently, this printing ink composition 1 was used as a viscosity adjusting solvent using npropyl acetate / isopropyl alcohol = 50/50, and Zaan Cup No. The viscosity was adjusted so as to be 15 seconds at 3, and diluted for use.

<Method for creating printed matter and laminated product>
The diluted ink of the obtained printing ink composition 1 is printed on acid-resistant paper (basic weight 320 g / m ² , manufactured by Oji Paper Co., Ltd.) using a baby printing machine of Iwase Printing Machinery Co., Ltd. with a conventional 30μ solid plate. 1P was obtained. Thereafter, immediately after the corona treatment is applied to the printed matter, low density polyethylene (Pedrocene 204, manufactured by Tosoh Corporation) is melted at a temperature of 310 to 320 ° C. and extruded to a thickness of 20 μm to obtain a desired laminated product 1L. It was.

[Examples 2 to 15, Comparative Examples 1 to 7]
In Examples 2 to 15 and Comparative Examples 1 to 7, printing ink compositions 2 to 21 for paper gravure rotation were produced in the same manner as in Example 1 at the blending ratios shown in Tables 2 and 3, respectively. For Examples 6, 11, 12, 13, 14, and Comparative Examples 1, 3, and 6, the polyester-based polyurethane resin varnish c1 was added to the structure of the ink composition. For Comparative Examples 4 and 5, water and ethylene glycol were used instead of glycerin, respectively. Further, printed materials 2P to 22P and laminated products 2L to 22L were prepared by the same printed material producing method as in Example 1. However, in Comparative Example 2, the ink stability was poor and a printed matter could not be prepared.

  The printing ink compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 7 and the laminate processed products were evaluated for ink stability and laminate strength, respectively. The evaluation method and evaluation criteria are shown below.

<Ink stability>
After storing the printing ink composition at 30 ° C. for 1 week, the degree of phase separation and precipitation was visually observed, and the viscosity was measured with Zahn Cup # 3. Evaluation was performed according to the following criteria. The practical level is Δ or more.
○: Phase separation and precipitation do not occur, and increase in viscosity is less than 1 second.
Δ: There is no phase separation and precipitation, but the viscosity increases for 1 to 5 seconds.
X: There is phase separation and precipitation, and the viscosity increases for 5 seconds or more.

<Blocking resistance>
The printed materials were stacked on the printing surface / non-printing surface and stored for 1 week in a storage environment of 40 ° C.-80% RH under a load of 10 N / cm ² , and then the stacked printed materials were peeled off. Evaluation was performed according to the following criteria. The practical level is Δ or more.
○: Tack does not occur and ink is not removed.
Δ: Tack occurs, but ink is not removed.
X: Ink removal occurs.

<Lamination strength>
The laminated product was cut to a width of 1.5 cm, peeled by 90 ° with an Intesco tensile tester, and the laminate strength was measured. The practical level is 1.5N or more.
(Double-circle): It is 2.5N or more and a base paper peels.
○: 2.0N to less than 2.5N Δ: 1.5N to less than 2.0N ×: less than 1.5N

  The printing ink compositions prepared in Examples 1 to 15 were both good in ink stability and blocking resistance, and a laminate processed product having good laminate strength could be obtained. On the other hand, in Comparative Examples 1, 3, 4, 5, and 6, a laminate strength defect of the laminated product occurred. Further, in Comparative Example 7, a poor blocking resistance occurred, and in Comparative Example 2, the printing ink composition had poor ink stability.

Claims (6)

A gravure rotary printing ink composition comprising a binder resin comprising a vinyl chloride-vinyl acetate copolymer (A) and an acrylic resin (B), glycerin, a colorant and a solvent,
A printing ink composition for paper gravure rotation, wherein glycerin is contained in an amount of 1 to 40% by weight based on the total solid weight of the ink.   2. The printing ink composition for gravure rotary rotation for paper according to claim 1, wherein the acrylic resin (B) has an acid value of 50 to 250 KOH mg / g and a weight average molecular weight of 5000 to 20000. When the solid content weight of the vinyl chloride-vinyl acetate copolymer (A) is W1, and the solid content weight of the acrylic resin (B) is W2,
The weight ratio of solid content W1 / W2 = 99/5 to 20/80, The printing ink composition for gravure rotation for paper according to claim 1 or 2.   When the binder resin further contains a polyester-based urethane resin (C) and the solid content weight is W3, the total solid content weight of the binder resin is W / W3 = 95/5 to 50/50. The printing ink composition for gravure rotation for paper of any one of Claims 1-3 characterized by these.   A printed matter obtained by printing the paper gravure rotary ink composition according to any one of claims 1 to 4 on a paper substrate.   A laminate product obtained by oxidizing the printed matter according to claim 5 and directly laminating a polyethylene resin without using an adhesive.