JP5588161B2 - Method for producing extender pigment dispersion composition and method for producing water-based printing ink composition - Google Patents

Description

  The present invention relates to a method for producing an extender pigment dispersion composition. More specifically, the present invention relates to a method for producing an extender pigment dispersion composition that can be reduced in both energy and time required for production.

  In recent years, the industry that prints on paper containers such as cardboard and cartons and various paper bags has been exposed to unprecedented price competition, reflecting the current situation, and reducing total costs by reducing raw material costs and streamlining printing operations. Is an urgent need. However, since there is a reasonable price for raw material costs, there is a natural limit to suppression. Therefore, rationalization of printing work is important for further cost reduction. And it becomes the pillar of rationalization of printing work to shorten the printing time, and it can be said that it is indispensable to increase the printing speed itself for that purpose. Furthermore, in order to increase the printing speed, it is necessary to use ink that can cope with it.

  For example, when the printing substrate is a wrapping paper, the ink is printed and then wound up through a guide roller of a printing machine. At this time, the printing surface comes into contact with the guide roller or the back surface of the wound paper. Even when the printing substrate is paperboard, after the ink is printed, the printed matter is stacked, and the printed surface and the back surface of another paperboard are in contact with each other. Such a time until the printing surface comes into contact with the guide roller or the back surface of the paper becomes shorter as the printing speed increases. Therefore, in order to increase the printing speed, the ink is required to have a performance that prevents the printed surface from being stained even if it comes into contact with a roller or a paper surface immediately after printing.

  Conventionally, when the printing substrate is a paper product such as a paper container or a paper bag, a water-based ink composition is used. The change in the state from when the ink is printed to when it is dried is as follows.

  Since the fiber of the paper made of cellulose has very high wettability with water, first, when the ink is transferred to the paper surface by printing, a liquid component such as an aqueous medium that penetrates the paper fiber and penetrates into the paper, Separation occurs with solid components such as colorants and resins that remain on the paper surface. The solid component becomes highly viscous as it is concentrated, further increases the fixing force due to the binding action of the resin, and forms a colored film that does not stain the printed surface even after winding or stacking after printing (generally called the set state, It can be said that the shorter the time to reach this state, the faster printing is possible). Thereafter, water and the like are evaporated, and the ink is completely dried.

  In the drying mechanism as described above, the time until the set state is reached is shortened (in the printing and ink industry, the length of time until the set state is usually referred to as dryness. For dry inks (sometimes referred to as very fast dry inks), it is necessary that the solid components on the paper be concentrated in a short time. For this purpose, two methods are conceivable in which the liquid component and the solid component are separated quickly or the solid component in the original ink is printed at a high concentration.

  First, it is relatively easy to quickly separate the liquid component and solid component of the ink, and in a system using an alkali-soluble resin that increases the permeability of the liquid component using a material that lowers the viscosity or lowers the surface tension. , The basic compound to be neutralized is volatile, the resin encapsulating the pigment is insolubilized and precipitated, and the liquid component is easy to evaporate (mainly low boiling point organic solvent, etc.) It's being used.

  However, increasing the permeability as a liquid component increases the spread of the paper surface and the depth of penetration into the paper, leading to the occurrence of fading and a decrease in density due to blurring and pigment sinking. In addition, the use of volatile basic compounds and the combined use of low-boiling organic solvents that easily evaporate cause them to evaporate and evaporate even on a printing press, making it difficult to maintain good printability due to thickening and the like. . Furthermore, the use of organic solvents is a cause of increasing environmental burden, and can be said to go against the trend of research and development.

  In order to solve the above problems, the applicant of the present application, for example, a technique that enables the use of low-viscosity ink (see, for example, Patent Document 1), suppresses changes in viscosity on a printing press, and has low permeability. In contrast, a technique for increasing the penetrating power of ink (see, for example, Patent Document 2) has also been proposed, but the time from printing to a set state has not been significantly shortened.

  Next, in the method of printing with a high concentration of solid components in the ink, simply increasing the concentration of all solid components uniformly results in drastic changes in viscosity on the printing press, making it difficult to produce stable and beautiful prints. It becomes. In addition, when the solid content of the pigment is increased individually, the relative amount of the resin of the binder component is decreased, the abrasion resistance of the ink film is lowered, and when the solid content of the alkali-soluble resin is increased, the liquid component is However, when the solid content of the aqueous resin emulsion is increased, good results are generally difficult to obtain, such as the fluidity of the ink being lowered.

  On the other hand, even if the extender pigment is increased, the change in the viscosity of the ink on the printing press is small, the fluidity is rather good, and the abrasion resistance of the ink film is not lowered. Furthermore, as expected, the drying effect can be improved, and increasing the concentration of solid components with extender pigments is a very effective method for designing fast-drying inks and ultra-fast-drying inks.

  Based on such knowledge, the applicant of the present invention has added basic pigments such as calcium carbonate and precipitated barium sulfate to the basic composition of the pigment for coloring, the aqueous resin and the aqueous medium as the aqueous ink composition for printing. Addition to form a super-fast drying ink, and a technique for suppressing the use of a specific basic compound for thickening during printing, which tends to decrease in performance, is disclosed (for example, see Patent Document 3). . However, this is a technique for improving the performance of ink that already contains extender pigments. In the future, in response to strong demands from the printing industry, and with increasing social momentum to reduce environmental impact, we can take a step forward and effectively disperse extender pigments with less energy and use them in ink compositions. It can be said that Kaga is a technology that contributes to industry.

  As a method for producing the extender pigment itself, for example, in typical calcium carbonate, limestone is generally wet pulverized (heavy calcium carbonate), or limestone is roasted into quick lime, and water is added to obtain a slaked lime solution. Thereafter, there is a method in which carbon dioxide gas is further reacted to insolubilize (colloid, light calcium carbonate).

  However, due to transportation problems, etc., it is supplied in a powder form through a drying process. In the drying process, calcium carbonate forms a strong aggregate and eventually becomes a powder with a large particle size (coarse particles). . Most of other extender pigments produced in an aqueous system also have a large particle size in the drying process. Therefore, conventionally, in order to include extender as an aqueous printing ink composition component, extender powder is kneaded for a long time with a disperser that requires high power energy, such as a bead mill, to a fine particle size before aggregation. And a method of adding an extender dispersion composition containing an alkali-soluble resin, an aqueous resin emulsion, or the like, which has been converted into an aqueous medium and further containing an alkali-soluble resin or an aqueous resin emulsion has been used. This method uses a strongly agglomerated powder of extender pigment, so it takes a lot of energy and time to disperse to fine particles, and the fine powder is scattered and the working environment deteriorates. Had the problem of doing.

JP 2003-221537 A JP 2001-146563 A JP 07-247455 A

  Accordingly, an object of the present invention is to provide a method for producing an extender pigment dispersion composition that can reduce the energy and time required for production and that has improved work environment.

  As a result of intensive studies to solve the above problems, the present inventors have found that a calcium carbonate slurry, a poly (ethylene oxide / propylene oxide) block polymer having a specific HLB value, and a heavy compound containing a basic compound are added. All of the above problems are solved by mixing the calcium carbonate slurry mixture with an alkali-soluble aqueous resin having a specific acid value and an aqueous resin emulsion having a specific acid value while stirring to produce an extender pigment dispersion composition. As a result, the present invention has been completed.

  The concept of the present invention is as follows.

  First, the first feature is to use the calcium carbonate dry powder in place of calcium carbonate slurry. In the calcium carbonate slurry prepared under the wet method, since water intervenes between the primary particles, an aggregate having a weak cohesive force is formed, and a force slightly larger than the cohesive force is applied. Dispersion is possible up to a state close to particles. Therefore, it is possible to finely disperse to a particle size equivalent to that of the conventional method only with a disperser driven with low power energy. However, since reaggregation occurs immediately as it is, further stabilization steps as a dispersion composition are required. In this stabilization method, an aqueous resin such as an alkali-soluble resin is added in the state of a high-concentration extender pigment to achieve an appropriate viscosity and dispersion stabilization of calcium carbonate. Contains an emulsion.

  Originally, according to such a first feature, the problem of the present invention should be solved by preparing an extender pigment dispersion composition using a stirrer used for ordinary stirring and mixing. However, when the final dispersion composition was formed, aggregates were generated, and as a result, a good extender pigment dispersion composition could not be obtained. This is because, when calcium carbonate is dispersed while applying mechanically high force from a dry powder to a fine particle state in the presence of a resin having high dispersion stability, the resin is adsorbed on the surface of calcium carbonate. From the slurry state, it is considered that the dispersion is unstable due to the absence of resin adsorption.

  Then, in order to further improve the dispersion stability of calcium carbonate, as a result of studying materials and mixing methods, (a) a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18 in a calcium carbonate slurry. (B) Before the calcium carbonate slurry is stirred and mixed with the aqueous resin varnish and aqueous resin emulsion, a basic compound is added to the calcium carbonate slurry to adjust the pH between the materials. It was found that the second feature of (c) using an aqueous resin emulsion of a resin having a specific acid value was added. Here, the timing of adding the basic compound to the calcium carbonate slurry of (b) may be either before or after treatment with a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18, and at the same time. . However, before stirring and mixing with the aqueous resin varnish and aqueous resin emulsion, the aggregation cannot be suppressed unless a basic compound is always added and mixed in the calcium carbonate slurry.

  Regarding the second feature, first, the dispersion stability of calcium carbonate is improved by (a), and in (b), in order to reduce the degree of change in pH between the respective materials, a basic property is added to the calcium carbonate slurry. By adding a compound, it is considered that when stirring and mixing, there is an effect of preventing a decrease in dispersion stability (called shock) of the system accompanying a change in pH.

  As described above, by adding the second feature to the first feature, all the problems of the present invention can be solved as a method for producing an extender pigment dispersion composition.

  That is, the present invention comprises (1) at least a calcium carbonate slurry, a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18, and a basic compound, and a basic compound-containing calcium carbonate slurry by stirring and mixing the three components. (2) Next, an alkali-soluble aqueous resin varnish containing an alkali-soluble aqueous resin having an acid value of 60 to 300 mgKOH / g, a basic compound and an aqueous medium, and an acid group-containing polymer emulsifier A step of mixing an aqueous resin emulsion having a total acid value of 10 to 110 mg KOH / g obtained by emulsion polymerization of a radically polymerizable monomer in the presence, and the basic compound-containing calcium carbonate slurry mixture with stirring. The present invention relates to a method for producing an extender pigment dispersion composition having the following.

  (1) After the step of obtaining the basic compound-containing calcium carbonate slurry mixture prepared by stirring and mixing the calcium carbonate slurry and a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18, The step is preferably a step of further stirring and mixing the basic compound with the mixture to obtain a basic compound-containing calcium carbonate slurry mixture.

  (1) The step of obtaining the basic compound-containing calcium carbonate slurry mixture is a mixture of three components of calcium carbonate slurry, poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18, and a basic compound. A step of obtaining a basic compound-containing calcium carbonate slurry mixture is preferred.

  In the step (1) of obtaining the basic compound-containing calcium carbonate slurry mixture, the calcium carbonate slurry and the basic compound are stirred and mixed to prepare a mixture, and then the poly (( (Ethylene oxide / propylene oxide) block polymer is preferably a step of stirring and mixing to obtain a basic compound-containing calcium carbonate slurry mixture.

  The calcium carbonate slurry is preferably a heavy calcium carbonate slurry.

  Moreover, this invention relates to the extender pigment dispersion composition obtained by the manufacturing method of the said extender pigment dispersion composition.

  Furthermore, the present invention relates to an aqueous printing ink composition containing the extender pigment dispersion composition, an aqueous resin, a colorant, and an aqueous medium.

  According to the method for producing an extender pigment dispersion composition of the present invention, there is provided a method for producing an extender pigment dispersion composition capable of reducing energy required for production and shortening the time and having improved working environment. be able to.

  The present invention will be described in detail below.

  First, the manufacturing method of the extender dispersion composition of this invention is demonstrated.

<Materials used in the method for producing extender pigment dispersion composition>
(Calcium carbonate slurry )
The calcium carbonate slurry that can be used in the present invention contains calcium carbonate particles in water with a solid content of about 10 to 80% by mass by a wet method. As such a calcium carbonate slurry, first, a heavy calcium carbonate slurry for papermaking in which natural limestone is wet-ground in water using a dispersant such as polycarboxylic acid can be used. The heavy calcium carbonate slurry obtained from this method is characterized by being inexpensive and easy to produce. Also, a colloidal (light) calcium carbonate slurry obtained by roasting limestone to quick lime, adding water to make a slaked lime solution, and further reacting with carbon dioxide gas can be used. Since colloidal calcium carbonate has a fine particle size and a uniform shape compared to heavy calcium carbonate, the resulting aqueous ink composition has a high gloss. The primary particle diameter of both heavy calcium carbonate and colloidal calcium carbonate is preferably 0.06 to 3.0 μm, more preferably 0.06 to 1.m, in terms of gloss and fluidity of the ink composition. The range is 0 μm.

(Poly (ethylene oxide / propylene oxide) block polymer)
The poly (ethylene oxide / propylene oxide) block polymer usable in the present invention includes two or more blocks, and each block is composed of polyethylene oxide or polypropylene oxide.

  The poly (ethylene oxide / propylene oxide) block polymer can be synthesized by a known method. For example, a polyethylene oxide polymer can react with propylene oxide to form a poly (propylene oxide / ethylene oxide / propylene oxide) block polymer. Alternatively, a polypropylene oxide polymer can react with ethylene oxide to produce poly (ethylene oxide). / Propylene oxide / ethylene oxide) block polymers can be formed.

  Specific examples of commercially available poly (ethylene oxide / propylene oxide / ethylene oxide) block polymers that can be used in the present invention include Adeka Pluronic series manufactured by Adeka Co., Ltd., New Pole EP manufactured by Sanyo Chemical Industries, Ltd. Series etc. are mentioned.

  The poly (ethylene oxide / propylene oxide) block polymer preferably has an HLB of 5 to 18 from the viewpoint of stability in an aqueous medium.

  The amount of the poly (ethylene oxide / propylene oxide) block polymer used is preferably in the range of 0.5 to 3 parts by mass with respect to 100 parts by mass of the heavy calcium carbonate slurry.

  When the amount of (ethylene oxide /) block polymer used is less than 0.5 parts by mass, aggregates are generated during the production of the extender pigment dispersion composition. On the other hand, when the amount exceeds 3 parts by mass, foaming and water resistance are caused. Is unfavorable because it decreases.

Here, the HLB represents the balance between the hydrophilic part and the lipophilic part of the molecule used in the field of surfactants, and the above HLB is the Griffin shown below. It can be obtained by applying the formula (an experimental value obtained from the measurement of the emulsification efficiency for a certain oil and a formula based on the mass fraction of the hydrophilic portion).
[Griffin Formula] HLB = (100/5) × hydrophilic group mass / (hydrophilic group mass + hydrophobic group mass)

  Usually, the polyethylene oxide chain is calculated as a hydrophilic group, and the propylene oxide chain is calculated as a hydrophobic group. Therefore, the above HLB of 5 to 18 corresponds to a compound having a polyethylene oxide chain mass ratio of 25 to 90% in the poly (ethylene oxide / propylene oxide) block polymer.

(Basic compound)
Examples of basic compounds that can be used in the present invention include organic basic compounds such as ammonia, triethylamine, monoethanolamine, triethanolamine, and N, N-dimethylethanolamine.

  It is preferable that the basic compound-containing heavy calcium carbonate slurry and the basic compound-containing colloidal calcium carbonate slurry have a pH value in the range of 8 to 8.5.

  In the basic compound-containing heavy calcium carbonate slurry and the basic compound-containing colloidal calcium carbonate slurry of the present invention, when the basic compound is contained so as to have a pH value of 8 to 8.5 under the above conditions, usually ink is used. Compared with other basic materials used as a material, the difference in pH is reduced, and the generation of aggregates can be suppressed. On the other hand, the pH value is preferably 8 to 8.5. When exceeding, it is not preferable because water resistance is lowered when it is finally used for ink.

(Alkali-soluble aqueous resin varnish )
As the alkali-soluble aqueous resin varnish that can be used in the present invention, an alkali-soluble resin having an acid value of 60 to 300 mgKOH / g, which has been conventionally used in aqueous printing ink compositions, is used as a basic compound. And dissolved in an aqueous medium can be used.

Alkali-soluble resin having an acid value of 60 to 300 mgKOH / g The alkali-soluble resin having an acid value of 60 to 300 mgKOH / g includes a radical polymerizable monomer containing an anionic group such as a carboxyl group and other co-polymers. Examples thereof include resins obtained by polymerizing a polymerizable radical polymerizable monomer. Among them, styrene-acrylic resins, styrene-maleic acid resins, acrylic resins, and the like are preferably used.

  For example, as the radical polymerizable monomer containing the anionic group, acrylic acid, methacrylic acid, maleic acid and monoester compounds thereof can be suitably used. Other copolymerizable radical polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl. (Meth) acrylic acid containing an aromatic ring such as (meth) acrylate alkylester compounds such as (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate (Meth) acrylic acid hydroxyalkyl ester compounds such as ester compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polypropylene glycol mono ( T) Acrylic acid ester compounds, styrene monomers such as styrene, α-methylstyrene, vinyltoluene and their derivatives, and dialkyl maleate compounds such as dimethyl maleate, diethyl maleate, and dibutyl maleate can be used. . In addition, these copolymer resins can be copolymerized with (meth) acrylamide, crotonic acid and its ester compound, itaconic acid and its ester compound, citraconic acid and its ester compound, acrylonitrile, etc., if necessary. A monomer may be contained as a copolymerization component.

  A method of synthesizing a resin using these radical polymerizable monomers is conventionally performed by a known method. Specific examples of the synthesis method include a mixture of the above monomers dissolved in an inert organic solvent such as an ester solvent such as butyl acetate, or a glycol solvent such as ethylene glycol monopropyl ether or ethylene glycol monobutyl ether. And an organic radical polymerization catalyst such as 2,2′-azobis (isobutyronitrile) such as t-butyl hydroperoxide, di-t-butyl peroxide, and the like, and polymerization is usually conducted at 40 to 120 ° C. However, the synthesis method is not particularly limited.

  In the alkali-soluble resin obtained by the above method, an acid value of less than 60 mgKOH / g is not preferable because it causes a problem that the dissolution stability of the resin in an aqueous medium is reduced. On the other hand, 300 mgKOH / g If it is larger, aggregates are easily generated during the production of the extender dispersion composition of the present invention, which is not preferable.

Basic compound As the basic compound, the above alkali-soluble resin is dissolved in an aqueous medium. Inorganic basic compounds such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, ethylamine, monoethanolamine, N Organic bases such as N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine Compound. These can be used alone or in admixture of two or more.

Aqueous medium As the aqueous medium, water or a mixture of water and a water-miscible organic solvent can be used.

  Examples of the water-miscible organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and glycerin, ethylene glycol Monoalkyl ethers of (poly) alkylene glycols such as monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoacetate, propylene glycol monoacetate Mono-fatty acid esters of (poly) alkylene glycols such as Etc., and the like. These water-miscible organic solvents can be used alone or in combination of two or more.

(Aqueous resin emulsion )
As the aqueous resin emulsion that can be used in the present invention, a radically polymerizable monomer is used in the presence of an emulsifier or a polymer emulsifier conventionally used in an aqueous printing ink composition having an acid value of 10 to 110 mgKOH / g. Aqueous resin emulsions such as acrylic aqueous resin emulsions obtained by polymerization, styrene-acrylic aqueous resin emulsions, and styrene-acrylic-maleic acid aqueous resin emulsions can be used.

  If the acid value of the aqueous resin emulsion is less than 10 mgKOH / g, it is not preferable because it makes it difficult to produce the emulsion. On the other hand, if it is more than 110 mgKOH / g, it is not preferable because aggregation occurs.

  These aqueous resin emulsions are synthesized by a conventionally known method. As a specific example of the synthesis method, a mixture of a radical polymerizable initiator and various radical polymerizable monomers described in the above alkali-soluble resin is dropped into water containing an emulsifier or a polymer emulsifier, and usually 40 Although the method etc. which superpose | polymerize at -120 degreeC can be illustrated, the synthesis method is not specifically limited.

  In addition, as an emulsifier, the molecular weight which has an acid value is about 5,000-50,000 from reasons, such as stability of emulsion polymerization, and the water resistance of the obtained aqueous printing ink composition, printability, or foam suppression. It is preferable to use an acrylic resin, a styrene-acrylic resin, a styrene-maleic acid resin or the like as a polymer emulsifier.

<Method for producing extender pigment dispersion composition>
In order to produce the extender pigment dispersion composition of the present invention, the order of addition of the above constituent materials is important. First, the calcium carbonate slurry (purchased container or another container such as a tank transferred from the container) is added to the polysilicic acid slurry. (Ethylene oxide / propylene oxide) block polymer and a basic compound are added and mixed by stirring to obtain a basic compound-containing calcium carbonate slurry mixture (in addition, calcium carbonate slurry and poly (ethylene oxide / propylene oxide) block The mixing order of the polymer and the basic compound is as follows: (1) The calcium carbonate slurry and the poly (ethylene oxide / propylene oxide) block polymer compound are stirred and mixed to prepare a mixture, and then the basic compound is further stirred and mixed. (2) Calcium carbonate slurry, HLB value ˜18 poly (ethylene oxide / propylene oxide) block polymer and three components of basic compound are stirred and mixed at the same time. (3) After preparing a mixture by stirring and mixing calcium carbonate slurry and basic compound, further HLB Any order, such as stirring and mixing the poly (ethylene oxide / propylene oxide) block polymer having a value of 5 to 18, may be used.

  Next, while stirring the basic compound-containing calcium carbonate slurry mixture, the alkali-soluble aqueous resin varnish and the aqueous resin emulsion are sequentially added, followed by a production method by stirring and mixing.

  The basic compound-containing calcium carbonate slurry mixture, the alkali-soluble aqueous resin varnish, and the aqueous resin emulsion may be mixed in any order.

  Next, an ink composition for water-based printing using the extender pigment dispersion composition of the present invention will be described.

<Constituent material of ink composition for water-based printing>
Pigments As the colored pigments constituting the aqueous printing ink composition of the present invention, various inorganic colored pigments and organic colored pigments that can be generally used in aqueous printing ink compositions and paints can be used.

  Specific examples of the inorganic pigment include colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, and calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide. And extender pigments such as talc. Furthermore, examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. The above pigments can be used alone or in combination of two or more.

  The content of the colored pigment is preferably 1 to 40% by mass in the aqueous printing ink composition.

Water-based binder resin As the water-based binder resin constituting the water-based printing ink composition of the present invention, alkali-soluble resin varnishes and water-based resin emulsions conventionally used in water-based printing ink compositions can be used.

  Examples of the alkali-soluble resin varnish include a varnish prepared by dissolving a vinyl resin having an acid value of 80 to 300 mgKOH / g containing an anionic group such as a carboxyl group in an aqueous medium using a basic compound. At least one selected from styrene-acrylic resin varnish, styrene-maleic acid resin varnish, acrylic resin varnish, and the like is preferable.

  If necessary, an aqueous resin emulsion conventionally used in an aqueous ink composition for water-based printing can be used as an aqueous binder resin in combination with these alkali-soluble resin varnishes.

  Specific examples of these aqueous resin emulsions include acrylic aqueous resin emulsion, styrene aqueous resin emulsion, styrene-acrylic aqueous resin emulsion, styrene-maleic acid aqueous resin emulsion varnish, styrene-acrylic-maleic acid aqueous resin. An emulsion varnish etc. can be illustrated.

<External pigment>
As the extender constituting the ink composition for water-based printing of the present invention, those described in the method for producing the extender pigment dispersion composition and, if necessary, other extender pigments can be used.

  The content of the extender pigment in the aqueous printing ink composition is preferably in the range of 2 to 17% by mass in terms of solid content.

<Aqueous medium>
The aqueous medium constituting the aqueous printing ink composition of the present invention is water alone or a mixture of water and a water-miscible solvent.

  Examples of water-miscible solvents include lower alcohols, polyhydric alcohols, and alkyl ethers and alkyl esters thereof. Specifically, lower alcohols such as methanol, ethanol, normal propanol and isopropanol, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Examples include ethylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoacetate, diethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

<Additives>
Furthermore, in the water-based printing ink composition of the present invention, in addition to the above components, as necessary, a pigment dispersant, a wax, an antiblocking agent, a wetting agent, a viscosity adjusting agent, a pH adjusting agent, an antifoaming agent, Various additives such as a surfactant can be appropriately selected and used.

<Method for producing aqueous ink composition for printing>
As a method for producing an aqueous printing ink composition using these various constituent materials of the aqueous printing ink composition of the present invention, a pigment, a pigment dispersing material such as an aqueous binder resin and a pigment dispersant, and water , After mixing with an aqueous medium such as a water-miscible solvent, the mixture is kneaded using various milling machines such as a bead mill, a pearl mill, a sand mill, a ball mill, an attritor, and a roll mill, and further, an extender pigment dispersion composition A method of adding and mixing the remainder of the predetermined constituent material can be exemplified.

  The water-based printing ink composition of the present invention obtained from the various constituent materials and manufacturing methods of the water-based printing ink composition of the present invention is used as a water-based flexographic ink mainly for cardboard. is there. Usually, the viscosity of the ink used in this printing method is controlled by the number of seconds flowing out of the Zahn cup or the like, and if necessary, it is water-based until it reaches an appropriate viscosity (Zan Cup No. 4 in 7 to 14 seconds). It is possible to print by diluting with a material used for a medium or the like. Furthermore, since recent printing tends to have high dilution and low viscosity, it is preferable to use an ink composition having a high solid content as much as possible in order to cope with such printing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.

  Unless otherwise specified, “part” and “%” in this example represent “part by mass” and “% by mass”.

<Basic Compound-Containing Heavy Calcium Carbonate Slurry Mixture of Example>
(Ethylene oxide / propylene oxide) block polymer and a basic compound are added to a slurry containing 75% heavy calcium carbonate having a primary particle size of 0.1 μm so as to have the ratio shown in Table 1, and mixed by stirring. The basic compound containing heavy calcium carbonate slurry mixture of Examples 1-9 was obtained.

<Heavy calcium carbonate slurry mixture of comparative example>
(Ethylene oxide / propylene oxide) block polymer and a basic compound are added to a slurry containing 75% heavy calcium carbonate having a primary particle size of 0.1 μm so as to have the ratio shown in Table 1, and mixed by stirring. The heavy calcium carbonate slurry mixture of Comparative Examples 1-3 was obtained.

<Example of basic compound-containing colloidal calcium carbonate slurry mixture>
(Ethylene oxide / propylene oxide) block polymer and basic compound are added to a slurry containing 75% of colloidal calcium carbonate with a primary particle size of 0.1 μm so that the ratio is as shown in Table 1, followed by stirring and mixing. The basic compound-containing colloidal calcium carbonate slurry mixture of Example 12 was obtained.

<Comparative Example Colloidal Calcium Carbonate Slurry Mixture>
(Ethylene oxide / propylene oxide) block polymer and basic compound were added to a slurry containing 75% colloidal calcium carbonate with a primary particle size of 0.1 μm so as to have the ratio shown in Table 1, followed by stirring and mixing. The colloidal calcium carbonate slurry mixture of Example 4 was obtained.

※１：いずれも三洋化成工業（株）社製
※２：塩基性化合物含有コロイド炭酸カルシウムスラリー
※３：コロイド炭酸カルシウムスラリー
実施例１〜９、１１：炭酸カルシウムスラリーとポリ（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーとを撹拌混合して混合物を調製した後、塩基性化合物を加え撹拌混合したもの
実施例１０：炭酸カルシウムスラリーとポリ（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーと塩基性化合物とを同時に撹拌混合したもの
実施例１１：炭酸カルシウムスラリーと塩基性化合物とを撹拌混合して混合物を調製した後、ポリ（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを加え撹拌混合したもの

* 1: All manufactured by Sanyo Chemical Industries, Ltd. * 2: Basic compound-containing colloidal calcium carbonate slurry * 3: Colloidal calcium carbonate slurry Examples 1 to 9, 11: Calcium carbonate slurry and poly (ethylene oxide / propylene oxide) ) Stirred and mixed with block polymer to prepare a mixture, then added with basic compound and stirred and mixed Example 10: Stirring calcium carbonate slurry, poly (ethylene oxide / propylene oxide) block polymer and basic compound simultaneously Example 11: A mixture prepared by stirring and mixing a calcium carbonate slurry and a basic compound, followed by adding a poly (ethylene oxide / propylene oxide) block polymer and stirring and mixing

<The basic compound containing heavy calcium carbonate slurry of Examples 1-11, the basic compound containing colloidal calcium carbonate slurry of Example 12, the calcium bicarbonate slurry of Comparative Examples 1-3, and the colloidal calcium carbonate slurry of Comparative Example 4 pH>
The pH of each slurry was measured with a pH meter (model: F-24, manufactured by Horiba, Ltd.). The results are shown in Table 1.

<External pigment dispersion composition>
The basic compound-containing heavy calcium carbonate slurry mixture of Examples 1 to 11 above, the heavy calcium carbonate slurry mixture of Comparative Examples 1 to 3 and Example 12 so as to be the blending composition and addition order of Tables 2 to 4 Example 1 A colloidal calcium carbonate slurry mixture containing a basic compound and a colloidal calcium carbonate slurry mixture of Comparative Example 4 were stirred and mixed with various alkali-soluble aqueous resin varnishes having different acid values and various aqueous resin emulsions having different acid values. To 19 and Comparative Examples 1 to 4 extender pigment dispersion compositions were obtained.

(Evaluation of mixability of extender pigment dispersion composition)
The extender pigment dispersion composition was screened with a 100-mesh net, and the mixing property was evaluated by the aggregate remaining in the net.
Evaluation criteria ○: No aggregate on the net Δ: Slight aggregate on the net ×: Many aggregate on the net

<Conventional extender pigment dispersion composition>
27 parts of g alkali-soluble water-soluble resin varnish with an acid value of 180 mg KOH / g, 28 parts of colloidal calcium carbonate, 34.5 parts of an aqueous resin emulsion with an acid value of 20 mg KOH / g, and 10.5 parts of water were mixed. The body pigment dispersion composition was obtained by kneading with a three-roll mill.

Water-based printing ink composition <Example of colored base ink production>
30 parts by mass of a pigment (phthalocyanine blue, B-15: 3), 25 parts by mass of an alkali-soluble water-soluble resin varnish (trade name: John Krill HPD-671, manufactured by Johnson Polymer Co., Ltd., solid content 25%) Then, a mixture of 2 parts by mass of isopropyl alcohol and 15 parts by mass of water is mixed and kneaded with a bead mill, and then 20 parts by mass of the above alkali-soluble water-soluble resin and 8 parts by mass of water are added and mixed to form a colored base ink. Was prepared.

<Water-based printing ink composition of Examples and Reference Examples>
30 parts by weight of a colored base ink, 30 parts by weight of an extender pigment dispersion composition (extreme pigment dispersion composition of the example, conventional extender pigment dispersion composition), an alkali-soluble water-soluble resin varnish (trade name: Jonkrill) 20 parts by mass of HPD-671, manufactured by Johnson Polymer Co., Ltd., solid content 25%), 20 parts by mass of aqueous resin emulsion (trade name: John Crill 631, manufactured by Johnson Polymer Co., Ltd., solid content 50%) The aqueous printing ink compositions of Examples and Reference Examples were obtained by mixing.

  In addition, evaluation was not performed about the thing of evaluation x in evaluation of the mixing property of an extender dispersion composition.

<Comparative Example 5>
30 parts by mass of colored base ink, 11.1 parts by mass of heavy extender pigment calcium slurry, alkali-soluble water-soluble resin varnish (trade name: Joncrill HPD-671, manufactured by Johnson Polymer Co., Ltd., solid content 25 %) And 20.8 parts by weight of an aqueous resin emulsion (trade name: Jonkrill 631, manufactured by Johnson Polymer Co., Ltd., solid content 50%) were added and mixed, and the aqueous printing ink composition of Comparative Example 5 was added and mixed. I got a thing.

(Evaluation of mixability of water-based printing ink composition)
The water-based printing ink compositions of Examples and Comparative Examples were screened with a 100-mesh net, and the mixing property was evaluated by the aggregate remaining on the net. The results are shown in Tables 2-4. About the mixing property of Comparative Example 5, many aggregates were observed in the net, and the evaluation was x.
Evaluation criteria ○: No aggregate on the net Δ: Slight aggregate on the net ×: Many aggregate on the net

(Print evaluation)
<Abrasion resistance>
The water-based printing ink composition obtained in the above examples and reference examples was developed on a K liner with a 0.15 mm Meyer bar, and a load of 500 g was applied using a Gakushin type friction resistance tester (manufactured by Daiei Chemical Seiki Co., Ltd.). The friction test was performed under conditions of 500 times. The results are shown in Tables 2-4.
Evaluation A: The addressed paper is not soiled and the printed matter is not scratched B: The addressed paper is soiled but the printed matter is not scratched C: The addressed paper is soiled and the printed matter is scratched (evaluation of friction resistance being C) Was not seen in this example or reference example)
(Note that A and B in the evaluation are practically acceptable ranges)

<Drying>
Under the environment of room temperature of 20 ° C. and relative humidity of 60%, the water-based printing ink compositions obtained in the above examples and reference examples were developed with a 0.15 mm Mayer bar on a K liner, and the dryness was evaluated by touching with a finger. The results are shown in Tables 2-4.
Evaluation A: Drying within 5 seconds after color development B: Drying for more than 5 seconds after color development (Those whose drying property was evaluated as B were not found in this example or reference example)

<Viscosity stability>
About the water-based printing ink composition obtained by the said Example and the reference example, the initial viscosity and the viscosity after 1-week preservation | save at 40 degreeC were measured with the B-type viscosity meter, and those viscosity ratios (storage at 40 degreeC for 1 week) The viscosity stability was evaluated from the following viscosity / initial viscosity. The results are shown in Tables 2-4.
Evaluation A: Viscosity ratio is 2.0 or less B: Viscosity ratio exceeds 2.0 and 5.0 or less C: Viscosity ratio exceeds 5.0 (Viscosity stability is evaluated as C) Was not seen in this example or reference example)

※４：評価が○、△のものについて水性印刷用インキ組成物を作成し印刷評価
構成成分
Ａ：顔料分散ベース
Ｂ：塩基性化合物含有重質炭酸カルシウムスラリー、塩基性化合物含有コロイド炭酸カルシウムスラリー、重質炭酸カルシウムスラリー、コロイド炭酸カルシウムスラリー
Ｃ：アルカリ可溶型水性樹脂ワニス（重量平均分子量１６，０００のスチレン−マレイン酸共重合体の２７質量部を、該共重合体の全量を中和するのに必要な量のアンモニアを含む水７３質量部中に加熱溶解させたもの）
Ｄ：水性樹脂エマルジョン（スチレン系エマルジョン、固形分５２％）

* 4: An ink composition for water-based printing was prepared for those having an evaluation of ◯ and △, and printing evaluation Component A: Pigment dispersion base B: Heavy calcium carbonate slurry containing basic compound, Colloidal calcium carbonate slurry containing basic compound, Heavy calcium carbonate slurry, colloidal calcium carbonate slurry C: alkali-soluble aqueous resin varnish (27 parts by mass of a styrene-maleic acid copolymer having a weight average molecular weight of 16,000 is neutralized with the total amount of the copolymer) And dissolved in 73 parts by mass of water containing the necessary amount of ammonia)
D: Aqueous resin emulsion (styrene emulsion, solid content 52%)

※５：評価が○、△のものについて水性印刷用インキ組成物を作成し印刷評価
構成成分
Ａ：顔料分散ベース
Ｂ：塩基性化合物含有重質炭酸カルシウムスラリー、塩基性化合物含有コロイド炭酸カルシウムスラリー、重質炭酸カルシウムスラリー、コロイド炭酸カルシウムスラリー
Ｃ：アルカリ可溶型水性樹脂ワニス（重量平均分子量１６，０００のスチレン−マレイン酸共重合体の２７質量部を、該共重合体の全量を中和するのに必要な量のアンモニアを含む水７３質量部中に加熱溶解させたもの）
Ｄ：水性樹脂エマルジョン（スチレン系エマルジョン、固形分５２％）

* 5: An ink composition for water-based printing was prepared for those having an evaluation of ◯ and △, and printing evaluation Component A: Pigment dispersion base B: Heavy calcium carbonate slurry containing basic compound, Colloidal calcium carbonate slurry containing basic compound, Heavy calcium carbonate slurry, colloidal calcium carbonate slurry C: alkali-soluble aqueous resin varnish (27 parts by mass of a styrene-maleic acid copolymer having a weight average molecular weight of 16,000 is neutralized with the total amount of the copolymer) And dissolved in 73 parts by mass of water containing the necessary amount of ammonia)
D: Aqueous resin emulsion (styrene emulsion, solid content 52%)

※６：評価が○、△のものについて水性印刷用インキ組成物を作成し印刷評価
構成成分
Ａ：顔料分散ベース
Ｂ：塩基性化合物含有重質炭酸カルシウムスラリー、塩基性化合物含有コロイド炭酸カルシウムスラリー
Ｃ：アルカリ可溶型水性樹脂ワニス（重量平均分子量１６，０００のスチレン−マレイン酸共重合体の２７質量部を、該共重合体の全量を中和するのに必要な量のアンモニアを含む水７３質量部中に加熱溶解させたもの）
Ｄ：水性樹脂エマルジョン

* 6: Aqueous printing ink compositions were prepared for those with an evaluation of ◯ and △, and printing evaluation Component A: Pigment dispersion base B: Heavy calcium carbonate slurry containing basic compound, Colloidal calcium carbonate slurry C containing basic compound : Alkali-soluble water-based resin varnish (27 parts by mass of styrene-maleic acid copolymer having a weight average molecular weight of 16,000 and water 73 containing ammonia in an amount necessary for neutralizing the total amount of the copolymer) (Heated and dissolved in part by mass)
D: Aqueous resin emulsion

Claims (6)

(1) A step of stirring and mixing at least a calcium carbonate slurry, a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18 and a basic compound to obtain a basic compound-containing calcium carbonate slurry mixture;
(2) Then, an alkali-soluble type resins having an acid value of 60~300mgKOH / g, a basic alkali-soluble aqueous resin varnish dissolved in an aqueous medium using a compound of the acid group-containing polymer emulsifier presence, obtained by emulsion polymerization of radically polymerizable monomer, and mixing reluctant such stirred aqueous resin emulsion, and the basic compound containing calcium carbonate slurry mixture of total acid number 10~110mgKOH / g A method for producing an extender pigment dispersion composition having (1) After the step of obtaining the basic compound-containing calcium carbonate slurry mixture prepared by stirring and mixing the calcium carbonate slurry and a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18, The method for producing an extender pigment dispersion composition according to claim 1, which is a step of further stirring and mixing a basic compound with the mixture to obtain a basic compound-containing calcium carbonate slurry mixture. (1) The step of obtaining the basic compound-containing calcium carbonate slurry mixture is a mixture of three components of calcium carbonate slurry, poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18, and a basic compound. The method for producing an extender pigment dispersion composition according to claim 1, which is a step of obtaining a calcium carbonate slurry mixture containing a basic compound. In the step (1) of obtaining the basic compound-containing calcium carbonate slurry mixture, the calcium carbonate slurry and the basic compound are stirred and mixed to prepare a mixture, and then the poly (( 2. The process for producing an extender pigment dispersion composition according to claim 1, wherein the ethylene oxide / propylene oxide) block polymer is stirred and mixed to obtain a basic compound-containing calcium carbonate slurry mixture. The method for producing an extender pigment dispersion composition according to any one of claims 1 to 4, wherein the calcium carbonate slurry is a heavy calcium carbonate slurry . Producing a mixture of an aqueous resin containing an aqueous binder resin , a colorant, and an aqueous medium ;
(1) A step of stirring and mixing at least a calcium carbonate slurry, a poly (ethylene oxide / propylene oxide) block polymer having an HLB value of 5 to 18 and a basic compound to obtain a basic compound-containing calcium carbonate slurry mixture; (2) Next, an alkali-soluble aqueous resin varnish obtained by dissolving an alkali-soluble resin having an acid value of 60 to 300 mgKOH / g in an aqueous medium using a basic compound, and presence of an acid group-containing polymer emulsifier Then, an aqueous resin emulsion having a total acid value of 10 to 110 mg KOH / g obtained by emulsion polymerization of a radical polymerizable monomer, and a step of mixing the calcium carbonate slurry mixture containing the basic compound with stirring Producing a pigment dispersion composition;
A method for producing a water-based printing ink composition , comprising the step of adding and mixing the extender dispersion composition to the mixture .