JP2013001755A - Aqueous inkjet recording ink for lamination and method for producing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous inkjet recording ink for lamination which has good dischargeability, can form an image as food wrapping material ink, and has excellent lamination aptitude.SOLUTION: The aqueous inkjet recording ink for lamination includes a pigment (a) and an aqueous resin (b). The aqueous resin (b) is a polyurethane resin produced through a process of reacting a chain extender. A mass ratio (b)/(a) between the pigment (a) and the aqueous resin (b) is 0.2-5.0. A method for producing a laminate using the aqueous inkjet recording ink for lamination is also provided.

Description

  The present invention relates to an aqueous inkjet recording ink, and more particularly to an aqueous inkjet recording ink for laminating that can be used as a laminating ink for packaging materials such as foods.

  Printing with an inkjet printer recording device is a method that ejects ink from nozzles and attaches it to the recording material. Unlike conventional printing, it is a printing method that does not use a plate, so it has become a small variety of products that have been in increasing demand in recent years. Demand is expanding as an on-demand printing method that can be supported.

  One of such high-demand applications for small quantities and many varieties is a packaging material used for packaging foods and beverages. Usually, the packaging material uses a plastic film that is a non-absorbing substrate. The packaging material is printed directly on the surface of the plastic film, and printed on the back surface of the plastic film that is an outer layer with product protection and various functions After that, there is a laminated packaging material in which an adhesive is applied on the printed layer and a sealant film that can be heat-sealed is bonded. The latter packaging material is excellent in aesthetics such as making use of the glossiness of the plastic film and preventing the scratch resistance of the ink, as well as strength to protect the contents from distribution, refrigeration, storage, heat sterilization, etc. Functions such as resistance to cracking, resistance to retort, and heat resistance can be imparted by combining a plurality of films, and this is the current mainstream.

Laminating suitability is particularly important for laminated packaging materials. If the laminate strength is insufficient, there is a possibility that the package is peeled off after being filled with food or the bag is broken from the heat seal portion.
Conventionally, gravure ink has been used as printing ink for food packaging materials. As a gravure ink having laminating suitability, for example, a water-based printing ink for laminating using a polyurethane resin having a hydrazine residue in the molecule and having no functional group that reacts with the hydrazine residue as a binder is known. (For example, refer to Patent Document 1).
However, the gravure ink requires a printing plate, and there has been a problem that it takes too much cost and labor to cope with the recent small quantity and variety. On the other hand, applying gravure ink to ink-jet ink has problems such as ink discharge properties and cannot be applied unconditionally.

JP-A-6-206972

  An object of the present invention is to provide a water-based inkjet recording ink for laminating which has good ejection properties, can form an image as an ink for packaging materials for foods, and has excellent laminating properties.

  As a result of intensive studies to solve the above problems, the present inventors have used an aqueous polyurethane resin chain-extended with hydrazine and specified a mass ratio of the pigment to be used and the aqueous polyurethane resin. It was found that by setting the range, a water-based inkjet recording ink for laminating can be obtained, which is excellent in ink ejection properties, can form an image as an ink for packaging materials for foods, and can provide sufficient laminating strength. .

That is, the present invention is an aqueous inkjet recording ink for laminating processing comprising (a) a pigment and (b) an aqueous resin,
The (b) aqueous resin is a polyurethane resin produced through a step of reacting a chain extender,
Provided is an aqueous inkjet recording ink for laminating, wherein the mass ratio (b) / (a) of the (a) pigment to the (b) aqueous resin is 0.2 to 5.0.

  The present invention also includes a step of forming a printing layer on a non-absorbent substrate by an inkjet recording method using the water-based inkjet recording ink described above, and a step of forming an adhesive layer on the printing layer. And a method for producing a laminate comprising a step of laminating a sealant film layer on the adhesive layer surface.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous property for laminating which can provide the laminated body applicable as a food packaging material which can form the image as an ink for packaging materials for foods with favorable discharge property, and was excellent in laminating property. Ink for ink jet recording can be obtained.

  Further, the laminate of the present invention is excellent in laminate suitability and is suitable as a food packaging material.

((A) Pigment)
The pigment used in the present invention is not particularly limited, and those usually used as pigments for water-based inkjet recording inks can be used. Specifically, it can be dispersed in water or a water-soluble organic solvent, and a known inorganic pigment or organic pigment can be used. Examples of the inorganic pigment include carbon black produced by a known method such as titanium oxide, iron oxide, a contact method, a furnace method, and a thermal method. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.

Specific examples of the pigment include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, Regal 400R, Regal 330R, Regal 660R, Mull 660R, Mull 660R Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are Color Black FW1, FW2, FW2V, FW18, FW200, S170, U , V, 1400U, Special Black 6 , 5, 4, 4A, NIPEX150, NIPEX160, NIPEX170, NIPEX180, and the like.
Specific examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.
Specific examples of pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, etc. It is done.
Specific examples of pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66, and the like.
In the present invention, a so-called self-dispersing pigment (surface-treated pigment) having a water dispersibility-imparting group on the pigment surface and capable of stably maintaining the dispersion state without a dispersant may be used. So-called capsule pigments (water-dispersible polymer-containing pigments) that can be stably maintained without a dispersant, or pigments dispersed with a dispersant may be used.

The pigment may be preferably dispersed in (b) an aqueous resin or a water-soluble solvent described later as a pigment dispersion dispersed by various pigment dispersants or surfactants.
The pigment dispersant is preferably an aqueous resin suitable for preparing a pigment dispersion. Preferred examples include acrylic resins such as polyvinyl alcohols, polyvinyl pyrrolidones, and acrylic acid-acrylic acid ester copolymers. Styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic Examples thereof include styrene-acrylic resins such as acid-acrylic acid ester copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins. .
The compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine. The amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
Of course, it is also possible to use a commercial item. As a commercially available product, Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, Ciba Specialty Chemicals EFKA series, etc. can be used.

((B) aqueous resin)
The (b) aqueous resin used in the present invention is a polyurethane resin produced through a step of reacting a chain extender. Specifically, it is an aqueous polyurethane resin obtained by neutralizing a urethane prepolymer obtained by reacting a diisocyanate with a carboxylic acid group-containing glycol and extending the chain with a chain extender. The chain extender is preferably hydrazine or a derivative thereof.
The polyurethane resin used in the present invention is produced as follows.
First, a urethane prepolymer is obtained by urethanizing diisocyanate with glycol and glycol having a carboxylic acid group.
Diisocyanates used at this time include aliphatic, alicyclic or aromatic diisocyanates. Examples of these are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane. Diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4-biphenylene diisocyanate, 3, , 3′-dimethoxy-4,4-biphenylene diisocyanate, 3,3′-dichloro-4,4-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene Diisocyanate, isophorone diisocyanate and the like.

  As the glycols for preparing the urethane prepolymer, low molecular weight glycols, high molecular weight glycols, polyester diols, polycarbonate diols, etc. may be used alone or as well known in urethane technology. In addition, low molecular weight glycols may be used in combination with polyester diols and high molecular weight glycols.

Examples of the low molecular weight glycols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, mexamethylene glycol, decamethylene glycol, octanediol, tricyclodehydride. There are candimethylol, hydrogenated bisphenol A, cyclohexane dimethal, and the like, and two or more of these may be mixed.
Examples of the high molecular weight glycols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  The polyester polyols are preferably the glycols and dicarboxylic acids, for example, linear aliphatic dicarboxylic acids having 4 to 12 carbon atoms. Specific examples thereof include succinic acid, adipic acid, azelaic acid, and sebacic acid. , Aliphatic dicarboxylic acids such as decanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl What is necessary is just what reacted dicarboxylic acid, such as dicarboxylic acid, diphenic acid, and aromatic dicarboxylic acids, such as its anhydride, and it manufactures by a well-known method. Moreover, not only esterification reaction but transesterification reaction may be sufficient. Polyester polyols can also be produced by transesterification using lower alkyl esters of glycols and dicarboxylic acids.

  The polycarbonate polyol may be any of those obtained by reacting the glycols with a carbonate compound such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, or the like. It is manufactured by the method.

  Examples of the glycols having a carboxylic acid group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like.

  The urethanization reaction is preferably performed in an organic solvent that is inert to isocyanate groups and has a high affinity for water, such as dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone, and tetrahydrofuran.

Next, the prepolymer is neutralized and chain-extended, and distilled water is added to obtain an aqueous polyurethane resin.
Examples of the neutralizing agent used for neutralization include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine; sodium hydroxide, potassium hydroxide, ammonia and the like.

Specific examples of hydrazine or a derivative thereof used for chain extension include hydrazine, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-hydrazine, and Examples thereof include hydrates thereof.
Polyols such as ethylene glycol and propylene glycol that are widely used as chain extenders for urethane prepolymers; ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, Aliphatic, alicyclic and aromatic diamines such as 2-methylpiperazine and isophoronediamine tend to be inferior in laminate suitability, which is an effect of the present invention.

The reason why the urethane resin subjected to hydrazine chain extension is excellent in laminating suitability is estimated as follows. That is, the polymer molecular terminal of the aqueous polyurethane resin obtained when the urethane prepolymer is chain-extended has a chemical structure of —NHNH ₂ —, and this structure contributes to adhesion and suitability for lamination. Estimated.

After chain extension, the organic solvent used in the urethanization reaction is desolvated by a known method if necessary, and then the polyurethane resin used in the present invention is obtained.
The polyurethane resin preferably has an acid value of 10 to 200 mgKOH / g per resin solid content. When the acid value is less than 10 mgKOH / g, when the urethane prepolymer reacted in an organic solvent is made aqueous by using a neutralizer, a chain extender, or distilled water, aggregates are likely to be formed, or the obtained aqueous polyurethane There is a possibility that the storage stability of the resin is poor. On the other hand, when the acid value exceeds 200 mgKOH / g, physical properties such as preferable durability and water resistance may not be obtained.

  Moreover, it is preferable to set suitably the glass transition point temperature (henceforth Tg) of the said polyurethane resin according to the desired use. For example, when printing the water-based inkjet recording ink of the present invention on a plastic film having flexibility such as for food packaging materials, the adhesion of the film when laminating and the flexibility of the packaging Because of the demand for flexibility, it is preferable that the glass transition temperature (hereinafter abbreviated as Tg) of the polyurethane resin is not so high. In order to achieve both good adhesion to a suitable film and flexibility, the Tg of the polyurethane resin used is preferably in the range of -80 ° C to 30 ° C, more preferably in the range of -50 ° C to 20 ° C. .

The polyurethane resin used in the present invention is usually obtained as an aqueous dispersion, but if its average particle size is too large, it will cause clogging of the head and cause ejection failure. For this reason, it is preferable that the average particle diameter of the polyurethane resin particles is as small as possible because the influence on ejection failure is small. Specifically, it is preferably in the range of 10 nm to 500 nm, and particularly preferably in the range of 10 to 100 nm.
Here, the particle diameter can be measured by a known and common centrifugal sedimentation method, laser diffraction method (light scattering method), ESA method, capillary method, electron microscope method, or the like. Preferable is measurement by Microtrac UPA using a dynamic light scattering method.

(Water-based inkjet recording ink for laminating)
The water-based inkjet recording for laminating process of the present invention, wherein the (a) pigment and the (b) aqueous resin are blended so that the mass ratio (b) / (a) is 0.2 to 5.0. Ink is obtained.
By setting the mass ratio within the above range, an ink having a good balance between laminating suitability and blocking resistance can be obtained. When the mass ratio is less than 0.2, the blocking resistance is poor, and when the mass ratio is more than 5.0, the laminate strength may be reduced.

  The method of blending the ink is not particularly limited, and can be performed by a conventionally used method. First, (a) a pigment (if necessary, (a) a pigment dispersion in which a pigment is dispersed with a pigment dispersant may be used), (b) an aqueous resin (various solvents after being adjusted by the above method) May be included), an aqueous solvent such as water or a water-soluble organic solvent, and, if necessary, a surfactant, a pigment dispersant, a viscosity modifier, an antifoaming agent, an antiseptic, etc. Examples of the dispersing and mixing method include a bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, an ultrahigh pressure homogenizer, and a pearl mill. If necessary, various additives may be further added thereafter.

  The water-soluble organic solvent used in the present invention is not particularly limited, but those that are miscible with water and can prevent clogging of an ink jet printer head are preferable. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butane Examples include diol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol, and the like. Among them, the inclusion of propylene glycol and 1,3-butyl glycol has safety and excellent effects in ink drying properties and ejection performance.

  Examples of the surfactant used in the present invention include acetylene surfactants. For example, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3- In addition to all, commercially available products include Surfinol 104, 82, 440, 465, 485, or TG (available from Air Products and Chemicals. Inc.), Olfin STG, Olfin E1010 (trade names manufactured by Nisshin Chemical Co., Ltd.) ) And the like.

(Laminate)
The water-based inkjet recording ink for laminating according to the present invention is used as a printing ink for laminates such as laminate films used for food packaging materials and the like.

  The plastic film that is a non-absorbing substrate used in the present invention is not particularly limited as long as it is used in food packaging materials, and known plastic films can be used. Specific examples include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films such as nylon, polystyrene films, polyvinyl alcohol films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, Examples include biodegradable films such as polylactic acid films. In particular, a polyester film, a polyolefin film, and a polyamide film are preferable, and polyethylene terephthalate, polypropylene, and nylon are more preferable. Moreover, the above-mentioned film coated with polyvinylidene chloride or the like for imparting a barrier property may be used, and if necessary, a film in which a deposited layer of a metal oxide such as aluminum or a metal oxide such as silica or alumina is used in combination. May be.

The plastic film may be an unstretched film, but is preferably stretched uniaxially or biaxially. Further, the surface of the film may be untreated, but those subjected to various treatments for improving adhesive properties such as corona discharge treatment, ozone treatment, low temperature plasma treatment, flame treatment, glow discharge treatment and the like are preferable.
The film thickness of the plastic film is appropriately changed according to the use. For example, in the case of a flexible packaging application, the film thickness is 10 μm to 100 μm as having flexibility, durability, and curl resistance. Preferably there is. More preferably, it is 10 micrometers-30 micrometers.

A printing layer is formed on the plastic film with the water-based inkjet recording ink for laminating according to the present invention.
Any conventionally known method can be used as the ink jet recording method. For example, a method of ejecting droplets using vibration of a piezoelectric element (a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element) or a method of using thermal energy can be given.

  Next, an adhesive layer for laminating is formed on the printed layer. The adhesive used for the adhesive layer is not particularly limited as long as it is generally used for laminating, and a known adhesive can be used. Specific examples include acrylic resin, urethane resin, urethane-modified polyester resin, polyester resin, epoxy resin, ethylene-vinyl acetate copolymer resin (EVA), vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, natural rubber, SBR. Adhesives such as synthetic rubber such as NBR, silicone rubber, etc., but preferably as one- or two-component curable polyether polyurethane adhesive, polyester polyurethane adhesive, polyester adhesive as an adhesive for dry lamination Good adhesive. As the adhesive for extrusion lamination, polyethyleneimine, alkyl titanate, polyurethane resin, urethane adhesive, and the like are preferable.

Next, a sealant film layer is formed by laminating.
As a laminating method, known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.
Specifically, in the dry lamination method, the adhesive is applied to one of the base films by the gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method). In addition, non-solvent lamination is a new film material on the surface immediately after applying the adhesive previously heated to room temperature to 120 ° C on a base film with a roll such as a roll coater heated to room temperature to 120 ° C. A laminated film can be obtained by laminating.
In the case of the extrusion laminating method, the organic solvent solution of the adhesive is applied to the base film as an adhesion assistant (anchor coating agent) with a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C. After being performed, a laminate film can be obtained by laminating the polymer material melted by the extruder. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.

  When the laminate thus obtained is used as a packaging material for food, the thickness of the plastic film, the thickness of the ink layer, and the thickness of the adhesive layer is controlled so that the thickness is 300 μm or less. It is preferable.

  Hereinafter, although the effect of the present invention is concretely explained using an example and a comparative example, the present invention is not limited to these examples. In the following description, parts and% indicate parts by weight.

(Production Example 1 Production Example of Aqueous Polyurethane Resin (b-1))
1000 parts of polycarbonate polyol “Nipporan N981” (average molecular weight = 1000) manufactured by Nippon Polyurethane Industry Co., Ltd. was dehydrated at 100 ° C. under reduced pressure. Thereafter, the mixture was cooled to 80 ° C., 1000 parts of ethyl acetate was added and sufficiently stirred to dissolve.
Next, 100 parts of 2,2′-dimethylolpropionic acid was added, and then 400 parts of tolylene diisocyanate was added and reacted at 75 ° C. for 5 hours to obtain a polyurethane prepolymer (b-1).
After confirming that the isocyanate value became 1.80 to 1.90%, the mixture was cooled to 40 ° C., neutralized by adding 75 parts of triethylamine, and then dissolved by adding 7000 parts of water. Subsequently, 36 parts of 80% hydrazine hydrazine was added as a chain extender to carry out a chain extension reaction.
Ethyl acetate was removed from the obtained translucent reaction product under reduced pressure at 30 to 60 ° C., water was added to adjust the concentration, and a stable translucent solution having a nonvolatile content of 20% and a Tg of −15 ° C. The aqueous polyurethane resin (b-1) which is an aqueous dispersion was obtained.

(Production Example 2 Production Example of Aqueous Polyurethane Resin (b-2))
Instead of the polycarbonate polyol in Production Example 1, the same operation as in Production Example 1 was carried out except that polytetramethylene ether glycol “PTMG-1000” (average molecular weight = 1000) manufactured by Mitsubishi Chemical Corporation was used. An aqueous polyurethane resin (b-2) which is a stable translucent aqueous dispersion at 20% min and Tg-50 ° C. was obtained.

(Preparation Example 1 Pigment dispersion (a-1) Cyan pigment dispersion)
Stir 20 parts of DIC Corporation Cyan Pigment “FANTOGEN BLUE FSJ-SD”, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water. Mixed. Next, after the kneaded meat was dispersed using a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a cyan pigment dispersion (a-1) adjusted to a pigment concentration of 15%.

(Adjustment Example 2 Pigment dispersion (a-2) Magenta pigment dispersion)
20 parts of magenta pigment “Fastogen Super Magenta RTS” manufactured by DIC Corporation, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water are mixed. did. Next, after kneading with a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a magenta pigment dispersion (a-2) adjusted to a pigment concentration of 15%.

(Preparation Example 3 Pigment dispersion (a-3) Yellow pigment dispersion)
20 parts of yellow pigment “Fast Yellow 7413” manufactured by Sanyo Dye Co., Ltd., 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water are mixed with stirring. did. Next, after the kneaded meat was dispersed using a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a yellow pigment dispersion (a-3) adjusted to a pigment concentration of 15%.

(Adjustment Example 4 Pigment dispersion (a-4) Black pigment dispersion)
Black pigment dispersion 20 parts of black pigment “Carbon Black # 960” manufactured by Mitsubishi Chemical Corporation, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, pure water 45 parts were stirred and mixed. Next, after kneaded with a bead mill, coarse particles were removed by a centrifugal separator, and pure water was added to obtain a black pigment dispersion (a-4) adjusted to a pigment concentration of 15%.

(Adjustment Example 5 Pigment dispersion (a-5) White pigment dispersion)
40 parts of white pigment “JR-804” manufactured by Teika Co., Ltd., 10 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water are mixed with stirring. A white pigment dispersion (a-5) was prepared by dispersing the kneaded meat using a bead mill and then adding pure water to adjust the pigment concentration to 38%.

(Solid content measurement method)
The weight of the evaporating dish (A), the total weight of the pigment dispersion dropped onto the evaporating dish (B), and the evaporating dish on which the pigment dispersion was dropped was allowed to stand in a dryer heated to 100 ° C. for 2 hours to evaporate water. The total amount (C) of the pigment dispersion and the evaporating dish that had been solidified was measured, and the solid content was determined by the following formula.

(Example 1) Production example of water-based inkjet recording ink (1) for laminating
6.7 parts of cyan pigment dispersion (a-1), 25 parts of aqueous polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, “Surfinol as a surfactant 440 "0.5 part and 47.6 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (1) for laminating.

(Example 2) Production example of water-based inkjet recording ink (2) for laminating
6.7 parts of cyan pigment dispersion (a-1), 15 parts of aqueous polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440 "0.5 part and 57.8 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (2) for laminating.

Example 3 Production Example of Aqueous Inkjet Recording Ink for Laminating (3)
20 parts of cyan pigment dispersion (a-1), 15 parts of aqueous polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440” 0 0.5 part and 44.5 parts pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (3) for laminating.

Example 4 Production Example of Aqueous Inkjet Recording Ink for Laminating (4)
20 parts of cyan pigment dispersion (a-1), 15 parts of polyurethane resin (b-1) of Production Example 1, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440” 5 parts and 44.5 parts of pure water were mixed. The mixed solution was filtered with a 0.5 μm filter to obtain an aqueous inkjet recording ink (4) for laminating.

Example 5 Production Example of Aqueous Inkjet Recording Ink for Lamination (5)
Cyan pigment dispersion (a-1) 20 parts, polyester polyurethane resin “Acryt WBR-601” synthesized by hydrazine chain extension manufactured by Taisei Fine Chemical Co., Ltd. (solid content 34%, Tg: −30 ° C.) 8.8 parts , 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, 0.5 part of a surfactant “Surfinol 440” and 56.1 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (5) for laminating.

(Example 6) Production example of water-based inkjet recording ink (6) for laminating
20 parts of cyan pigment dispersion (a-1), a polyether polyurethane resin “Acryt WBR-016U” (solid content 35%, Tg: −20 ° C.) 8.6 synthesized by hydrazine chain extension manufactured by Taisei Fine Chemical Co., Ltd. 8.6 Part, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, 0.5 part of a surfactant “Surfinol 440” and 50.9 parts of pure water were mixed. The mixed solution was filtered with a 0.5 μm filter to obtain an aqueous inkjet recording ink (6) for laminating.

Example 7 Production Example of Aqueous Inkjet Recording Ink for Laminating (7)
46.7 parts of magenta pigment dispersion (a-2), 15 parts of polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440” 0.5 part and 17.8 parts of pure water were mixed. The mixed solution was filtered with a 0.5 μm filter to obtain an aqueous inkjet recording ink (7) for laminating.

(Example 8) Manufacturing example of water-based inkjet recording ink (8) for laminating
26.7 parts of yellow pigment dispersion (a-3), 15 parts of polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440” 0.5 part and 37.8 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (8) for laminating.

(Example 9) Production example of water-based inkjet recording ink (9) for laminating
30 parts of black pigment dispersion (a-4), 15 parts of polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440” 0. 5 parts and 34.5 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (9) for laminating.

Example 10 Production Example of Aqueous Inkjet Recording Ink for Laminating (10)
26.3 parts of white pigment dispersion (a-5), 15 parts of polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant (Surfinol 440) 0.5 part and 38.2 parts of pure water were mixed. The mixed solution was filtered with a 0.5 μm filter to obtain an aqueous inkjet recording ink (10) for laminating.

(Comparative Example 1 Manufacturing Example of Water-based Inkjet Recording Ink for Lamination (H1))
6.7 parts of cyan pigment dispersion (a-1), 30 parts of polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440” 0.5 part and 42.8 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (H1) for laminating.

(Comparative Example 2 Production Example of Water-based Inkjet Recording Ink for Lamination (H2))
20 parts of a cyan pigment dispersion (a-1), a polyester polyurethane resin “hydran APX-101H” not chain-extended with hydrazine manufactured by DIC Corporation (solid content: 44.3%, Tg: 17 ° C.) 15 Part, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, 0.5 part of a surfactant “Surfinol 440” and 44.5 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (H2) for laminating.

(Comparative Example 3 Production Example of Water-based Inkjet Recording Ink for Lamination (H3))
20 parts of a cyan pigment dispersion (a-1), 15 parts of a polyester polyurethane resin “Hydran AP-30F” (solid content 20%, Tg: 61 ° C.) not chain-extended with hydrazine manufactured by DIC Corporation, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, 0.5 part of a surfactant “Surfinol 440” and 44.5 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (H3) for laminating.

(Comparative Example 4 Production Example of Water-based Inkjet Recording Ink for Lamination (H4))
39.5 parts of white pigment dispersion (a-5), 11.3 parts of polyurethane resin (b-2) of Production Example 2, 10 parts of propylene glycol, 10 parts of 1,3-butylene glycol, surfactant “Surfinol 440 "0.5 part and 28.7 parts of pure water were mixed. The mixed solution was filtered through a 0.5 μm filter to obtain an aqueous inkjet recording ink (H4) for laminating.

(Comparative Example 5 Production Example of Water-based Inkjet Recording Ink for Lamination (H5))
Mix 100 parts of water-based gravure ink “Marine Plus G R507 Primary Color Indigo (C1)” manufactured by DIC Graphics Co., Ltd., 21 parts of ethanol and 9 parts of pure water to obtain an aqueous inkjet recording ink (H5) for laminating. It was.

[Evaluation of the physical properties]
(Storage stability test)
The viscosity of the inks of Examples 1 to 10 and Comparative Examples 1 to 4 was measured with an E-type viscometer (TV-20, manufactured by Toki Sangyo Co., Ltd.), and the particle size distribution meter (Microtrac UPA-150, manufactured by Nikkiso Co., Ltd.) After measuring the 50% particle size, the sample was placed in a glass sample bottle, and the lid was closed and sealed, and left in a constant temperature bath at 60 ° C. After 30 days, the sample bottle was taken out of the thermostatic chamber, and the viscosity and 50% particle size of the ink were measured. Evaluation was judged as follows.
○: Change rate of viscosity / 50% particle size is less than 10% Δ: Change rate of viscosity / 50% particle size is 10% or more and less than 20% ×: Change rate of viscosity / 50% particle size is 20% or more, or Ink separation occurs

(Discharge test)
An ink jet printer having a piezo head with a maximum driving frequency of 7.6 KHz and a resolution of 360 DPI (360 dots per 25.4 mm) was evaluated by ejecting onto a PET film (Ester E-5100 manufactured by Toyobo Co., Ltd.). .
Evaluation was judged as follows.
After printing equivalent to 10 sheets of A4 solid, a check pattern is printed and non-ejection nozzles are evaluated. ○: Non-ejection nozzles less than 1% △: Non-ejection nozzles 1% or more and 5% or less

(Lamination test)
(1) Adjustment of adhesive 10 parts of DIC Graphics adhesive “Dick Dry LX-401”, 10 parts of DIC Graphics curing agent “SP-60”, 60 parts of ethyl acetate as a curing agent The mixture was stirred and the adhesive was adjusted.

(2) Manufacturing method of laminated body Bar coater No. is used for PET film (Ester E-5100 manufactured by Toyobo Co., Ltd.) and OPP film (FOR30 manufactured by Phutamura Chemical Co., Ltd.) used for food packaging materials. 4, the inks of Examples 1 to 10 and Comparative Examples 1 to 4 were applied, and the ink was dried by leaving it in a dryer heated to 100 ° C. for 3 minutes.
After the ink dries, the bar coater no. 10 was applied with the adhesive prepared in the above (1), dried with hot air from a dryer for 10 seconds to dry the adhesive, and covered with a CPP film (Pyrene P-1128 manufactured by Toyobo Co., Ltd.) The roll temperature was pasted with a laminator set at 40 ° C. The laminated product was left in a constant temperature bath at 40 ° C. for 48 hours to cure the adhesive.

(3) Laminate strength test The laminate of (2) in which the adhesive was sufficiently cured was cut into a length of 200 mm and a width of 15 mm, and the bonded portion was peeled off by about 30 mm. The slightly peeled part was further peeled with a tensile tester (TENSILON RTM-25 manufactured by Orientec Co., Ltd.), and the adhesive strength of the laminate layer was measured.
Evaluation was judged as follows.
○: Strength when peeling a laminated product is 1 N / 15 mm or more Δ: Strength when peeling a laminated product is less than 0.5 N / mm to less than 1 N / 15 mm x: Strength when peeling a laminated product Less than 0.5N / 15mm

(4) Testing of blocking resistance A PET film (Ester E-5100 manufactured by Toyobo Co., Ltd.) and an OPP film (FOR30 manufactured by Framura Chemical Co., Ltd.) used for food packaging are coated with a bar coater no. The ink was applied at 4 and left in a dryer heated to 100 ° C. for 1 minute to dry the ink. After the ink was dried, the printing surface and the film back surface were overlapped, and a pressure of 9.8 × 10 ⁴ Pa (1 kgf / cm ² ) was applied thereto. After leaving for 24 hours, it was peeled off and evaluated for blocking resistance.
Evaluation was judged as follows.
○: There is no setback on the back of the film when the stacked film is peeled. Δ: About 10% setback occurs on the back of the film when the stacked film is peeled. ×: The back of the film when the stacked film is peeled off. Overset of about 10% occurs

Tables 1 to 3 show ink formulations, and Tables 4 to 6 show physical property evaluation results.

From this result, the water-based inkjet recording ink for laminating of the example obtained excellent storage stability, dischargeability, and laminate strength.
On the other hand, Comparative Example 1 is an example in which the mass ratio (b) / (a) between the (a) pigment and the (b) aqueous resin exceeds 5, but the laminate strength was lowered. Moreover, although the comparative example 4 is an example below 0.2, it was inferior to blocking resistance.
Moreover, although the comparative examples 2 and 3 are examples which used the polyurethane resin which is not chain | stretched with hydrazine, it was inferior to blocking resistance.
Comparative Example 5 is an example in which gravure ink is applied to inkjet ink, but ejection was not possible.

[Manufacturing Method of Multicolored Printed Laminate]
(Example 11)
PET film (Toyobo Co., Ltd.) used as a packaging material for food in an ink jet printer having a piezo head having the maximum driving frequency of 7.6 KHz and resolution of 360 DPI (360 dots per 25.4 mm). Ester E-5100) and OPP film (FOR30, FORMURA CHEMICAL CO., LTD.) Were discharged and left in a dryer heated to 100 ° C. for 1 minute to dry the ink. After the ink of Example 3 was dried, the ink of Example 7 was ejected and dried in the same manner as in Example 3, and the same operations were performed for the inks of Examples 8, 9, and 10 for each color ink. A multicolored print was produced. In accordance with the laminating test method, a bar coater no. After the adhesive was applied and cured using No. 10, the laminate strength was measured. As a result, the evaluation was good.

Claims (6)

(A) Pigment, (b) Water-based inkjet recording ink for laminating process containing water-based resin, wherein (b) water-based resin is a polyurethane resin produced through a step of reacting a chain extender, A water-based inkjet recording ink for laminating, wherein the mass ratio (b) / (a) of (a) pigment to (b) aqueous resin is 0.2 to 5.0. The water-based inkjet recording ink for laminating according to claim 1, wherein the chain extender is hydrazine or a derivative thereof. The water-based inkjet recording ink for laminating according to claim 1 or 2, wherein the polyurethane resin is a polyether-based polyurethane resin, a polycarbonate-based polyurethane resin, or a polyester-based polyurethane resin having a glass transition temperature of 20 ° C or lower. Using the water-based inkjet recording ink for laminating according to any one of claims 1 to 3, a step of forming a printing layer on a non-absorbent substrate by an inkjet recording method, and adhesion on the printing layer The manufacturing method of the laminated body characterized by having the process of forming a layer, and the process of laminating a sealant film layer on the said adhesive layer surface. The manufacturing method of the laminated body of Claim 4 whose thickness of the said laminated body is 300 micrometers or less. The method for producing a laminate according to claim 4 or 5, wherein the non-absorbing substrate is a plastic film.