JP3394828B2 - Aqueous printing ink composition for paper - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous printing ink set for paper.
For products, more specifically, it has high gloss and vivid hue.
Water-based printing ink for paper with sufficient printability and resistance
Composition. 2. Description of the Related Art Recently, cardboard boxes, carton cases, and the like have been developed.
About printed matter of paper bags such as paper containers and shopping bags
Are increasingly demanding for cosmetics and are used for
Printing inks, in addition to high gloss and vivid hue,
Good printability that can be used for fine printing is required.
You. The ink used to print these paper containers and paper bags is almost
Most of them are water-based and are used as ink binder resins.
Styrene monomer with high refractive index in the presence of surfactant
Aqueous resin emulsion copolymerized with acrylic monomer
Using, it is possible to obtain printed matter with high gloss
Is already known. Further, an aqueous resin emulsion of this type
The higher the content, the higher the gloss of the printed matter,
On the other hand, friction resistance is poor due to a decrease in the cohesive strength of the ink film.
In addition, foaming is likely to occur, and furthermore, due to poor fluidity
For example, it is not possible to respond to high-definition printing due to deterioration in printability,
Had many problems. Therefore, the cohesive force of the ink film
High glossy styrene monomer and soft
To polymerize the acrylic monomer in the
Aqueous-type water-based styrene-acrylic resin emulsion
John, JP-A-4-275315, JP-A-5-5-2
It is disclosed in Japanese Patent Publication No. 95048 and the like. These methods
Ink containing the aqueous resin emulsion obtained from
Gives excellent prints such as gloss and water resistance, but still foams
And the problem of poor printability has not yet been resolved.
That is the current situation. [0004] Therefore, an object of the present invention is to solve the problem.
Has high gloss and vivid hue, low foaming,
Water-based printing ink for paper that can be used even in high-definition printing
It is to provide a composition. [0005] That is, the present invention provides a face
Material, aqueous binder resin varnish and water
In the aqueous printing ink composition for paper to be formed, the aqueous
As a binder resin varnish, a component: acid value 80 to 300, number average molecular weight 3,000 to
Alkaline with 200,000 polymer emulsifier (a1) dissolved
In the aqueous solution of the compound, the styrenic monomer was converted to (a2)
Methacrylate (a3), other acrylic acid or meth
Assuming that the ester compound of crylic acid is (a4),
Obtained by emulsion polymerization of the monomer in the range of the following weight ratio.
And the glass transition temperature of the emulsion polymer is 50 ° C or lower.
Above, an aqueous resin emulsion having an average particle diameter of 30 to 150 nm.
Rejon, {(a2) + (a3) + (a4)} :( a1) = 92: 8-6
0:40 {(a2) + (a3)}: (a4) = 70:30 to 100:
0, and b component: acrylic resin having an acid value of 5 to 300, styrene-A
Krill resin, styrene-maleic acid resin and styrene
-At least one acrylic-maleic resin is
Water-soluble resin varnish dissolved in an aqueous solution of potassium compound
Contains as an essential component, and furthermore, the solid content of the component a to the component b
Is 1.0: 0.05 to 1.0: 1.
Water-based printing ink composition for paper, characterized by being 0
Related. [0006] As a more preferred embodiment, the following (1) and
And (2) a water-based printing ink composition for paper. (1) As the component a, the polymer emulsifier (a1)
Resin, styrene-acrylic resin, styrene-maleic
Acid resin and styrene-acrylic-maleic acid resin
Aqueous resin emulsion using at least one of
The aqueous printing ink composition for paper used. (1) As the component a, (a2): {(a3) + (a4)} = 7
Aqueous resin emuljo in a weight ratio of 0:30 to 100: 0
An aqueous printing ink composition for paper using an ink. [Working and Examples] Making the ink film have high gloss
As a means, an aqueous resin emulsion of a high refractive index polymer is used.
It is well known to use, but high refractive index polymers
Having a high Tg and forming a film as it is
Can not. Therefore, monomers that increase the refractive index of the polymer
Components and monomer components that form a flexible polymer
Core-shell type aqueous resin emulsion
Is used as an ink binder.
The type of Ip has poor resolubility,
Dry film easily accumulates, causing poor transfer and plate jam
Cause. Furthermore, this type of aqueous resin emulsion
Ink containing a lot of
In addition, the amount of ink transferred from the printing plate to the paper surface is reduced.
In terms of gloss, emulsion particles form
The loss of gloss due to layering can be avoided
Absent. [0008] For these reasons, high gloss and high definition
An ink composition that can be applied to the required fields of printed matter is not available.
Not been. In contrast, the aqueous resin emulsion of the present invention
John is an artist whose film-forming components are used as polymer emulsifiers.
Since it is a luka-soluble resin, the ink film
The compound can be redissolved in an aqueous solution of the compound. Therefore, printing
The dried film of the ink on the plate is
Dissolves in water-soluble ink, so it does not accumulate on the plate.
And can sufficiently cope with high-definition printing. The water of the present invention
Ink using a water-soluble resin emulsion
Even if the content of marsion increases, the degree of fluidity decrease
However, good printed matter can be obtained because of the low quality. In terms of gloss, emulsion particles
Set the glass transition temperature of the particles to a range that does not form a film at room temperature
As a result, the emulsion remains as particles in the ink film
Present invention, and there is no decrease in gloss due to film formation.
Let's set the emulsion particle size to the most glossy range
To give printed products higher gloss and sharper hues.
Was given. Hereinafter, the present invention will be described in more detail.
You. Pigment The pigment used in the present invention is generally used in aqueous inks.
Useable organic, inorganic or extender pigments can be used. This
The usual amount of these pigments used is based on the total amount of the aqueous ink composition.
On the other hand, 1 to 20% by weight of the organic pigment system,
In the machine pigment system, it is 1 to 50% by weight. Aqueous binder resin varnish Essential component of aqueous binder resin varnish used in the present invention
Is a) a radically polymerizable monomer in the presence of a polymer emulsifier
Aqueous resin emulsion obtained by emulsion polymerization of
And b) an acid value of 5 to 350 in an aqueous solution of an alkali compound.
Is a water-soluble resin varnish obtained by dissolving a water-soluble resin. A) Aqueous resin emulsion First, the aqueous resin emulsion of the present invention has a
Existence of polymer emulsifier having a boxyl group or an acid anhydride group
In the presence, styrene monomer and / or methyl methacrylate
Rate to other copolymerizable radicals as needed
Aqueous resin obtained by emulsion polymerization by adding a polymerizable monomer
Marjon. As the polymer emulsifier of the present invention,
Kuryl resin, styrene-acrylic resin, styrene-male
Inic acid resin and styrene-acrylic-maleic acid resin
Can be used. Here, acrylic resin, styrene-acrylic
Resin, styrene-maleic acid resin and styrene-
Lil-maleic acid resin is an acrylic monomer
Copolymer resin, styrene monomer and acrylic monomer
Copolymer resin with styrene monomer and maleic acid monomer
Copolymer resin with styrene monomer,
A copolymer tree of a trialkyl monomer and a maleic acid monomer
It is fat. In addition, acrylic monomer, styrene monomer
And maleic acid-based monomers are the following monomer components:
Minutes. Acrylic monomer: (meth) acrylic acid
And an alkyl ester having 1 to 18 carbon atoms,
Is an alkylamide having 1 to 18 carbon atoms,
Specifically, methyl (methyl)
T) acrylate, ethyl (meth) acrylate,
Chill (meth) acrylate, hexyl (meth) acryle
Octyl (meth) acrylate, lauryl (meth)
TA) acrylate, stearyl (meth) acrylate
G, methyl (meth) acrylamide, ethyl (meth)
Acrylamide, butyl (meth) acrylamide, hex
Sil (meth) acrylamide, 2-hydroxyethyl
(Meth) acrylate and the like. Styrene monomer: Styrene and its styrene
Derivatives, specifically α-methylstyrene, chlors
Tylene, vinyltoluene and the like can be mentioned. Maleic monomer: (anhydride) maleic acid and its charcoal
Alkyl ester having a prime number of 1 to 18, carbon number of 1 to 18
Alkyl amide, hydroxyalkyl having 2 to 4 carbon atoms
Esters, specifically, monomethyl malate, dimethyl
Methyl malate, monoethyl malate, diethyl maleate
G, monobutyl malate, monooctyl malate, mono
Acid of a polymer emulsifier obtained by copolymerizing these monomers such as -2-hydroxyethyl malate
Value is 80-300, preferably 150-250, number average
The molecular weight is 3,000 to 200,000, preferably 1
It is in the range of 000 to 100,000. The acid value of the polymer emulsifier is within the above range.
As the size decreases, the solubility of the polymer emulsifier in water decreases.
On the other hand, if it exceeds the above range, the water resistance of the ink
Is undesirably reduced. In addition, the number of the polymer emulsifier
When the average molecular weight is smaller than the above range, polymer emulsification
The effect as an agent is reduced, while it is larger than the above range.
Is preferred because the solubility of the polymer emulsifier in water decreases.
I don't. In order to dissolve this polymer emulsifier in water,
Ammonia, organic alcohol
Min, alkali metal hydroxides and the like.
Typically, organic amines such as diethylamine and triethyl
Alkylamines such as
Ethanolamine, ethylethanolamine, diethyl
Ethanolamine, diethanolamine, triethanol
Alkanolamines such as ruamine, alkali metal hydroxide
Examples include sodium hydroxide, potassium hydroxide and the like.
Can be Among them, at room temperature to improve drying
Alternatively, it is desirable that the substance be easily volatilized by a slight heating. The required amount of the alkali compound is as follows:
Amount required for stable presence of polymer emulsifier in water
As a lower limit, approximately 80% of the amount of neutralization is set as the lower limit, and approximately
The upper limit is twice. Meanwhile, the polymer emulsifier
Radical polymerizable monomer used in emulsion polymerization in the presence of
(Emulsion polymerization component) is a styrene monomer, methyl
Use taclyate alone or in combination
Other copolymerizable activites as needed.
Use of lylic acid or methacrylate in emulsion polymerization
Up to 30% by weight of all monomers to be used. As the emulsion polymerization component, a styrene-based
Is used to obtain the gloss of the ink composition targeted by the present invention.
Uses more than 70% by weight of all emulsion polymerization components
It is desirable to do. The above polymer emulsifier, alkali compound
Products, radical polymerizable monomers used in emulsion polymerization
As a method for producing an aqueous resin emulsion,
Ester esters such as ethyl acetate and isopropyl acetate;
Ketones such as seton and methyl ethyl ketone, lower alcohol
In organic solvents such as glycols, glycols and their derivatives,
Monomer for obtaining a polymer emulsifier in the presence of a polymerization initiator
After polymerizing the components, the organic solvent is distilled off,
A solid resin soluble in the liquid is obtained. Next, the solid is added in the presence of an alkali compound.
Dissolve the resin in water to make a polymer emulsifier,
Mixture of used radical polymerizable monomer and polymerization initiator
To obtain an aqueous resin emulsion by emulsion polymerization.
Methods are available. In addition, as a polymerization initiator, for example,
For example, potassium persulfate, sodium persulfate, ammonium persulfate
Persulfates such as benzoyl hydroperoxide
Organic peroxides such as side, azobisisobutyronitrile
Azo compounds such as
Used as a redox initiator in combination with the base agent
You can also. The polymer obtained by the emulsion polymerization of the present invention comprises:
It is necessary that the glass transition temperature be 50 ° C. or higher. Heavy
If the glass transition temperature of the coalescence is less than 50 ° C, the drying process
Emulsion particles can be easily formed into a film with good gloss
Cannot be obtained. In addition, the aqueous solution of the present invention
In resin emulsion, polymer emulsifier and emulsion polymerization
The weight ratio of the obtained polymer to the polymer emulsifier is 8 to 40.
The polymer is 60 to 92% by weight based on the weight%. The weight ratio of the polymer emulsifier is within the above range.
The smaller the dispersion, the lower the dispersion of the aqueous resin emulsion in water.
The qualitative properties and the fluidity of the ink are reduced.
If it is large, the gloss of the ink is undesirably reduced. Sa
Furthermore, the average of the aqueous resin emulsion used in the present invention
The particle system has a size of 30 to 150 nm, more preferably 80 to 1 nm.
It is in the range of 20 nm. Average particle size of aqueous resin emulsion
When the diameter is smaller than the above range, the ink concealing property,
The sense of degree decreases, while if it exceeds the above range, the
The gloss and printability of the print are undesirably reduced. B) Water-soluble resin varnish The water-soluble resin varnish used in the present invention includes
Polymerization of ril, styrene and maleic acid monomers
Acrylic resin, styrene-acrylic resin,
Styrene-maleic acid resin and styrene-acryl
-Alkaline alkali-soluble resin such as maleic acid resin
It was dissolved in an aqueous solution of the compound. This alkali is acceptable
As a method for producing a soluble resin, the aqueous resin emulsion
The same methods can be used as for the production of the polymeric emulsifier. Further, in order to obtain a water-soluble resin varnish,
The acid value is 5 to 300 as the alkali-soluble resin.
It is necessary. Acid value is smaller than the above range
And the solubility of the resin in water decreases, while increasing
In addition, the drying properties and water resistance of the ink are reduced. The present invention
The number average molecular weight of the alkali-soluble resin is 5,000
~ 200,000, glass transition temperature should be over 60 ℃
Is preferred. The number average molecular weight of the alkali-soluble resin is as described above.
If it is smaller than the range, the rub resistance of the ink decreases,
On the other hand, as the size increases, the solubility of resin, fluidity of ink, etc.
Is undesirably reduced. Further, the glass transition temperature is 60
When the temperature is lower than ℃, the blocking resistance of the ink is reduced.
Not preferred. Therefore, the number of
Average molecular weight and glass transition temperature are out of the preferred ranges.
Other inks so that the ink performance does not deteriorate.
Material handling is required. The alkali soluble of the present invention
Compound used to dissolve water-soluble resin in water
The alkali compound can be used as the
As for the amount of the potassium compound, the alkali-soluble resin
The amount of neutralization required for stable presence
The lower limit is 80% and the upper limit is approximately twice the amount of neutralization
It is. Optional Ingredients The present invention may further comprise, if necessary, other aqueous binder resin.
Varnishes, for example aqueous shellac varnish, aqueous casein varnish
Varnish, aqueous rosin maleic resin varnish, aqueous polyester
Use terresin varnish, water-soluble cellulose varnish, etc. in combination
be able to. Further, the aqueous printing ink composition of the present invention
Are commonly used wax, defoamer, pigment dispersant,
Add various additives such as bridging agents, water-miscible organic solvents, etc.
be able to. Aqueous resin emulsion and water-soluble resin varnish
Aqueous resin emulsion and water-soluble resin crocodile in the present invention
Weight ratio of water-based resin emulsion
John: water-soluble resin varnish = 1.0: 0.05-1.
0: 1.0, more preferably 1.0: 0.1 to 1.0:
The range is 0.7. Here, the aqueous resin emulsion
The content of the water-soluble resin varnish is less than the above range
When this happens, the fluidity and rub resistance of the ink decrease.
If this happens, the gloss and color developability of the ink will be poor. The above
The lower limit of the water-soluble resin varnish is
It is desirable to apply this method when the amount of the polymer emulsifier is large.
No. Next, a method for producing an ink using the above-described materials will be described.
I do. First, a coloring agent, an aqueous binder resin varnish (mainly water
Soluble resin varnish) and, if necessary, pigment dispersant
The normal ink production equipment (eg, ball mill,
Using a lighter, sand mill, etc.)
After that, a predetermined material can be added and mixed to produce.
The aqueous printing ink composition obtained by the above method,
High gloss, clear hue, less foaming, and higher
Water-based printing ink composition for paper that can be used even in fine printing
Things. Examples and Comparative Examples Hereinafter, the present invention will be described more specifically with reference to examples.
However, the present invention is not limited to these examples.
Unless otherwise specified, “parts” and “%”
Represents "parts by weight" and "% by weight". The aqueous emmanulsion resin No. 1-26
Manufacturing stirrer, thermometer, condenser, nitrogen gas inlet pipe and
In a reactor equipped with a dropping funnel, 100 parts of cellosolve acetate were added.
While stirring and heating under reflux while introducing nitrogen gas.
100 parts of the monomer having the composition shown in Table 1 and diter as a polymerization initiator
A mixture of 2 parts of shary butyl hydroperoxide
The solution was dropped from the dropping funnel over 3 hours. Further dripping end
Thereafter, polymerization was carried out at reflux temperature for 3 hours to complete the reaction.
Distillation of rosolve was carried out to obtain a polymer emulsifier having an acid value of 65 to 312.
To obtain copolymer resins 1 to 10 to be used. Shown in Table 1
You. [Table 1] Next, an emulsifier, a thermometer, a condenser,
Table 2 shows a reactor equipped with a raw gas introduction pipe and a dropping funnel.
-1, 2-2 according to the composition of
0 and 1.2 equivalents of ammonia in advance of the neutralization amount of the water-soluble resin
Was dissolved in water and dissolved by heating at 80 to 90 ° C.
After that, maintain the temperature at 65-80 ° C under stirring and nitrogen gas introduction.
Furthermore, the monomer 10 of the emulsion polymer having the composition shown in Tables 2-1 and 2-2
0 parts, ditertiary butyl hydro
A mixture of 0.5 to 2.5 parts of peroxide is added dropwise.
The solution was dropped over 3 hours. After the dropping, 65-
Emulsion polymerization was carried out at 80 ° C. for 3 hours to complete the reaction.
Adjust the aqueous resin to 5% and adjust the aqueous resin
m) No. 1-26 were obtained. Table 2-1 and Table 2-2
You. [Table 2-1] [Table 2-2] In this embodiment, an emulsifier (bath) having a variable rotation speed is used.
BT-102035D, manufactured by Iotron Co., Ltd., stirring blade
35mm diameter, 20μm clearance)
The average particle size of the fat emulsion is adjusted to
Rotation speed of the emulsifier according to the degree of stress of the conductive medium
And the polymerization initiator concentration. In addition, aqueous
Resin emulsion No. 17, 23 and 25 are aggregates
Is extremely difficult to use as a binder for ink.
Was not used for the preparation of the ink. Aqueous resin Emanlusion No. 27 production emulsifier, thermometer, condenser, nitrogen gas inlet pipe and
In a reactor equipped with a dropping funnel, 40 parts of styrene, acrylic
4 parts of ruic acid, 5 parts of sodium dodecylbenzenesulfonate, vinegar
Charge a mixture of 1 part acid soda and 560 parts ion-exchanged water
While maintaining the pH at 7-8, ammonium persulfate (10
% Solution), and gradually heating was continued.
The polymerization is carried out at 70 ° C. Internal temperature rises by 5 ° C due to initial exothermic reaction
After about 350 hours, drop in 350 parts of styrene monomer
It was gradually added by a lower funnel. In this reaction, pH is adjusted to p by decomposition of sodium acetate.
14% ammonia as needed to keep H7-8
Ammonium persulfate (5%) solution added to near water
35 ml of the H7.5 preparation solution is continuously added dropwise in small portions.
Thereafter, the temperature was maintained at 70 ° C. for 2 hours, and the above-mentioned 14% ammonia was added.
PH of ammonium persulfate (5%) solution added to water
35 ml of the preparation solution of 7.5 are added twice every 30 minutes.
The styrene / acrylic acid copolymer obtained in this way is
As a seed, add ammonium persulfate (5%) and
Using redox system of sodium bisulfite (2.5%)
And adding 2ethylhexyl acrylate to the core component
40 parts were dropped so as to be 10% by weight, and the solid content was 4%.
5%, average particle size 140 nm, pH 8.5
Marjon (aqueous resin Em) No. 27 was obtained. Aqueous resin emulsion no. 28 emulsifier, thermometer, condenser, nitrogen gas inlet tube and
In a reactor equipped with a dropping funnel, 100 parts of water and emulsifier
Polyoxyethylene nonyl phenyl ether (ethoxy
0.7 part and dodecylbenzene sulfone
Charge 0.8 parts of sodium acid and heat at 80-90 ° C
After that, maintain the temperature at 65-80 ° C under stirring and nitrogen gas introduction.
100 parts of styrene and ditertiary as a polymerization initiator
Drop of 1-butyl hydroperoxide mixture
The solution was dropped over 3 hours. After the dropping, 6
The reaction is completed by emulsion polymerization at 5 to 80 ° C for 3 hours.
Aqueous resin emansion (aqueous resin)
Em) No. 28 was obtained. Water-soluble resin varnish No. Production water-soluble resin varnish Nos. 1. Production stirrer, cooling pipe, thermometer, nitrogen gas introduction pipe and dropper
60 parts of ethyl acetate were charged into a reactor equipped with
After heating to 5 to 78 ° C, introduce nitrogen gas
10 parts acrylic acid, methyl methacrylate 10, ethyl
10 parts of acrylate, 10 parts of styrene and initiation of polymerization
0.2 part of ditertiary butyl peroxide as an agent
Was dropped from the dropping funnel over 3 hours. Further
After completion of the dropwise addition, polymerize at reflux temperature for 3 hours to complete the reaction
Then, cellosolve acetate is distilled off to obtain a water-soluble resin varnish.
To obtain a copolymer resin 11 having an acid value of 195. Stirring
In a container equipped with a machine, 40 parts of the crushed product of the copolymer resin 11,
1.2 equivalents of ammonia, which is the neutralized amount of the copolymer resin 11,
Prepare 60 parts of water and dissolve by heating at 80 ° C with stirring
And a water-soluble resin varnish having a solid content of 40%. 1 was obtained. Water-soluble resin varnish No. 2, stirrer, cooling tube, thermometer, nitrogen gas inlet tube and dropper
60 parts of ethyl acetate were charged into a reactor equipped with
After heating to 5 to 78 ° C, introduce nitrogen gas
25 parts of monobutyl maleate, 15 parts of styrene and
Ditertiary butyl peroxide as polymerization initiator
0.2 parts of the mixture was dropped from the dropping funnel over 3 hours.
Was. After the completion of the dropwise addition, the mixture was polymerized at the reflux temperature for 3 hours,
When the reaction is completed, the cellosolve acetate is distilled off and the water-soluble resin
No. 204 copolymer resin No. used as varnish 1
2 was obtained. In a container equipped with a stirrer, place the copolymer resin 12
40 parts of crushed material, 1.2 equivalents of neutralization amount of copolymer resin 12
60 parts of water containing ammonia, and stir 8
Heated and melted at 0 ° C, water-soluble resin varnish N with a solid content of 40%
o. 2 was obtained. Water-soluble resin varnish No. 3. Manufacturing stirrer, cooling pipe, thermometer, nitrogen gas inlet pipe and dropper
60 parts of ethyl acetate were charged into a reactor equipped with
After heating to 5 to 78 ° C, introduce nitrogen gas
20 parts of monobutyl maleate, 5 parts of ethyl acrylate
Parts, 15 parts of styrene and ditasia as a polymerization initiator.
Drops a mixture of 0.2 parts of low-butyl peroxide
Over 3 hours. After the addition is completed, reflux
The reaction is completed by polymerizing at a temperature for 3 hours.
Is distilled off to obtain an acid value of 15 used as a water-soluble resin varnish.
Thus, a copolymer resin 13 was obtained. In a container equipped with a stirrer,
40 parts of the crushed product of the copolymer resin 13,
Charge 60 parts of water containing 1.2 equivalents of ammonia for neutralization
And heat and dissolve at 80 ° C with stirring to obtain a solid content of 40%.
Water-soluble resin varnish No. 3 was obtained. Examples 1 to 21 and Comparative Examples 1 to 11
Pigment and water-soluble resin crocodile according to the composition of Tables 3-1 and 3-2
Mixture for 30 minutes with paint conditioner
After that, other materials were added and mixed, and
The aqueous printing ink compositions of Comparative Examples 1 to 11 were obtained. Face here
As a fee, First Gen Blue TGR (Dainippon Inn)
(Manufactured by Ki Chemical Industry Co., Ltd.). Evaluation of Examples 1 to 21 and Comparative Examples 1 to 11
Gloss, Chromogenicity of Valent Examples 1 to 21 and Comparative Examples 1 to 11,
Evaluation of friction resistance, flowability and foaming properties
Are shown in Tables 3-1, 3-2 and 3-3. Each evaluation test
The test was performed by the following method. In addition, gloss, abrasion resistance,
For fluidity, C or more, and for coloration, B or more
It is an object of the invention. A gloss test ink was coated with a 0.15 mm Mayer bar using a coated cardboard.
(CRC 230g, manufactured by Rengo Co., Ltd.)
The gloss was evaluated from the measurement result of the 0-degree specular gloss value. A: The measured value is 40 or more, B: The measured value is 35 or more and less than 40, C: The measured value is 30 or more and less than 35, D: The measured value is less than 30. The color developing test ink was applied to a K liner (R) with a 0.15 mm Mayer bar.
AK 180g made by Rengo Co., Ltd.)
Paper (CRC 230g, manufactured by Rengo Co., Ltd.)
Print and evaluate the color development from the degree of color difference on both test papers
did. A: No color difference is observed at all, B: Marking with K liner slightly compared to coated cardboard
Turbid color is seen in the printing part. C: In the printing part with K liner compared to coated cardboard
The color tone of the paper is clearly seen, or white blur occurs. The rub resistance test ink was prepared using a 165-line hand proofer.
Liner (RAK 180g, made by Rengo Co., Ltd.)
Prints and prints the Gakushin-type dyed material.
(Made by Taisung Science Seiki Seisakusho Co., Ltd.)
The test was performed under a load of 200 g as a K liner.
The abrasion resistance was evaluated from the state of contamination of the backing paper. A: Contamination of the applied paper even after 500 rubs
No staining, B: No contamination of the patch after 200 rubs
However, contamination was found on the backing paper after 500 rubs. C: Slight contamination was observed on the backing paper with 200 rubs. D: Contamination was observed on the backing paper with 200 rubs.
Streak-like scratches are made. Using a fluid type B viscometer, rotation at 30 rpm and 60 rpm
The fluidity is better as the ink viscosity ratio at speed is closer to 1
The liquidity was evaluated by judging that it was. A: The viscosity ratio of 30 rpm / 60 rpm is 1.2 or less.
B: The viscosity ratio of 30 rpm / 60 rpm exceeds 1.2
1.5 or less C: The viscosity ratio of 30 rpm / 60 rpm exceeds 1.5
thing. The foaming test ink was applied for 12 seconds with Zahn Cup No. 4 (manufactured by Rigaud).
After diluting with water so as to obtain 50g in a paper cup
Then, the mixture was stirred with a stirrer at a rotation speed of 1500 rpm, and
Transfer to a 00 ml graduated cylinder
The foamability was evaluated from the disappearance time. A: Bubbles are less than 3 ml and disappear within 90 seconds
B: The height of bubbles is 3 ml or more, but bubbles are within 90 seconds
C: The height of the bubbles is 3 ml or more, and the bubbles disappear within 90 seconds.
do not do. [Table 3-1] [Table 3-2] [Table 3-3] As described above, as specified in the embodiments, the present invention is specified.
Aqueous resin emulsion and water-soluble resin as binder
Aqueous ink composition has high gloss and vivid hue.
Low foaming, and can be used even in high-definition printing
It is an aqueous printing ink composition for paper.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-157611 (JP, A) JP-A-54-126290 (JP, A) JP-A-48-73488 (JP, A) 145251 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/10

Claims (1)

(57) [Claim 1] In an aqueous printing ink composition for paper mainly composed of a pigment, an aqueous binder resin varnish and water, the aqueous binder resin varnish includes: a component: an acid value of 80 to 80; 300, number average molecular weight 3,000-
200,000 styrene in an aqueous alkali compound solution in which at least one polymer emulsifier (a1) selected from acrylic resin, styrene-acrylic resin, styrene-maleic acid resin and styrene-acryl-maleic acid resin is dissolved. When the monomer is (a2), methyl methacrylate is (a3), and other acrylic acid or methacrylic acid ester compound is (a4), emulsion polymerization of these monomers in the following weight ratio And obtained, and
Aqueous resin emulsion having a glass transition temperature of the emulsion polymer of 50 ° C. or more and an average particle diameter of 30 to 150 nm, {(a2) 10 (a3) 10 (a4)} :( a1) = 92: 8 to 60: 40 {(a2) 10 (a3)} :( a4) = 70: 30-100: 0, (a2): {(a3) 10 (a4)} = 70: 30-100: 0, and component b: acid A water-soluble resin varnish obtained by dissolving at least one of an acrylic resin having a valency of 5 to 300, a styrene-acrylic resin, a styrene-maleic acid resin and a styrene-acryl-maleic acid resin in an aqueous solution of an alkali compound; Further, the weight ratio of the solid content of the component a to the solid content of the component b is 1.0: 0.05 to 1.0:
An aqueous printing ink composition for paper, which is set to 1.0.