JP7394581B2 - Manufacturing method of polyurethane resin - Google Patents

Description

The present invention relates to a method for producing polyurethane resin.

As described in Patent Document 1, it is known that a urethane prepolymer is subjected to chain extension and reaction termination, and then a ketone compound is reacted with the terminal amino group of the obtained polyurethane resin to perform ketimination. There is. According to such a method of synthesizing a ketiminated polyurethane resin, odor is reduced and it is said that the resin has excellent viscosity stability.
According to this synthesis method, even though the irritating odor caused by acetone is reduced, the low molecular weight chain extender and reaction terminator present in the system are also converted into ketimine.
Another odor is generated due to the ketiminated low molecular weight chain extender and reaction terminator, so in the end, the odor of the composition as a whole could not be suppressed sufficiently.
Furthermore, although the effect on viscosity stability is the result of suppressing the lowering of the molecular weight of polyurethane during storage, the ink composition is affected by the ketiminated low molecular weight chain extender and reaction terminator that remain without being completely removed. A problem arose in that the stability over time deteriorated when used as paints or paints.

Furthermore, as described in Patent Documents 2 and 3, it is known that a polyurethane polyurea resin powder for slush molding can be obtained by reacting a ketimine compound obtained from a diamine and a ketone with a urethane prepolymer in an aqueous solvent. It is being
Furthermore, in particular, Patent Document 2 describes that a urethane prepolymer is chain-extended with a two-molecular condensate of a ketone in the presence of water and a dispersion stabilizer.

JP 2017-2184 Publication Japanese Patent Application Publication No. 2012-251010 JP2011-208128A

The problem to be solved by the present invention is to eliminate the residual odor and decrease in stability over time, which are inherent in polyurethane polyurea resin compositions in which terminal amino groups are ketiminated.

The present inventors have discovered that the above problems can be solved by employing a specific method for producing polyurethane polyurea resin.
That is, the present invention
1. Synthesize urethane prepolymer from diol compound and diisocyanate compound,
Next, the urethane prepolymer is reacted with a chain extender and/or a reaction terminator in which the amino groups of a polyamine compound are ketiminated with a ketone compound under solvent-free conditions in a polar organic solvent to form a ketimine terminal. A method for producing a polyurethane polyurea resin.
2. 1. The chain extender and/or reaction terminator is a chain extender and/or reaction terminator ketiminated with one or more types selected from acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol as the ketone compound. A method for producing a polyurethane polyurea resin having a ketimine terminal as described above.
3. The method for producing a polyurethane polyurea resin with a ketiminated terminal according to 1 or 2, wherein only the chain extender is ketiminated;
It is.

According to the present invention, the ink composition and the printed matter do not have the odor peculiar to ketimine, and furthermore, when the ink composition is made into an ink composition, it can exhibit the effects of being excellent in stability over time.

The production method of the present invention uses a ketimine compound obtained under specific conditions as a chain extender and/or reaction terminator, and reacts it with a urethane prepolymer in a specific solvent, thereby producing the polyurethane polyurea resin itself. However, it does not generate the odor of ketimine, and has excellent stability over time when stored in a solution state for ink compositions, paints, etc.
Hereinafter, the method for producing the polyurethane polyurea resin of the present invention will be explained.

(Polyurethane polyurea resin)
The polyurethane polyurea resin obtained by the method of the present invention is a polyurethane polyurea resin having at least one type selected from a primary amino group and a secondary amino group at the end of the molecule. The amino group is ketiminated.
More preferably, it is a polyurethane polyurea resin having a hydroxyl group and at least one type selected from a primary amino group and a secondary amino group at the end of the molecule.
As these polyurethane polyurea resins, polyurethane resins obtained by synthesizing a urethane prepolymer by reacting an organic diisocyanate compound and a polymeric diol compound and reacting this with the following chain extender and reaction terminator are preferably used. can.

<Synthesis of urethane prepolymer>
The urethane prepolymer is obtained by reacting the following organic diisocyanate compound with a polymeric diol compound.
(Organic diisocyanate compound)
Examples of the organic diisocyanate compound include 1,3- and/or 1,4-phenylene diisocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, tolylene diisocyanate, etc. aromatic diisocyanate compounds, dicyclohexylmethane 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), methylcyclohexylene diisocyanate (hydrogenated TDI), Alicyclic diisocyanate compounds such as isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate (HDI), ethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and m- and/or aromatic aliphatic diisocyanate compounds such as p-xylylene diisocyanate (XDI), α, α, α', α'-tetramethylxylylene diisocyanate, and these organic diisocyanate compounds may be used alone or in combination of two or more. Can be used in combination. Among them, alicyclic diisocyanates, aliphatic diisocyanates, and araliphatic diisocyanates are more preferred.

(Polymer diol compound)
Examples of the polymer diol compound include one or more dibasic acids such as adipic acid, sebacic acid, and phthalic anhydride, and ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, - Polyester diol compounds such as polyester diols and polycaprolactone diols obtained by condensation reaction with one or more glycols such as methyl-1,5-pentanediol, as well as polyethylene glycol, polypropylene glycol, etc. and polyether diol compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide. These polymeric diol compounds can be used alone or in combination of two or more. Among these, 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1000 to 8000, which is obtained by a condensation reaction of adipic acid and 3-methyl-1,5-pentanediol, is preferable, and more preferably 3-methyl-1,5-pentylene adipate diol having a molecular weight of 1,000 to 4,000 is preferred.

(Bio polyester diol compound)
With environmental considerations in mind, biopolyester diol compounds may be synthesized from materials containing plant-derived components.
A polyurethane polyurea resin can be obtained by reacting a polyester diol compound containing a biopolyester diol compound with an isocyanate compound, and the above-mentioned polyester diol compound not derived from plants can also be used in combination.
Therefore, a biopolyester polyol (biomass polyester polyol) obtained by reacting a short chain diol compound having 2 to 4 carbon atoms with a carboxylic acid component can be used. In the biopolyol component, at least one of the short chain diol compound and the carboxylic acid component is preferably derived from a plant, and even more preferably both are derived from a plant.
The plant-derived short chain diol compound having 2 to 4 carbon atoms is not particularly limited. For example, the short chain diol compound may be 1,3-propanediol, 1,4-butanediol, ethylene glycol, etc. obtained from plant materials by the following method. These may be used in combination.
1,3-propanediol can be produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (eg, corn, etc.). Compared to the 1,3-propanediol compound produced by the EO production method, the 1,3-propanediol compound produced by biomethods such as the fermentation method described above produces useful by-products such as lactic acid, and moreover, It is also possible to keep costs low. 1,4-butanediol can be produced by producing succinic acid obtained by producing glycol from plant resources and fermenting it, and hydrogenating this. Furthermore, ethylene glycol can be produced from bioethanol obtained by conventional methods via ethylene.

Plant-derived carboxylic acids are not particularly limited. For example, carboxylic acids include sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid, and the like. These may be used in combination. Among these, it is preferable that the carboxylic acid component contains at least one selected from the group consisting of sebacic acid, succinic acid, and dimer acid. Further, 0.05 to 0.5 parts by mass of malic acid may be contained per 100 parts by mass of sebacic acid.
The biopolyol component can be produced as a 100% plant-derived biopolyester polyol by appropriately condensing a plant-derived short chain diol compound and a plant-derived carboxylic acid. Specifically, polytrimethylene sebacate polyol is obtained by direct dehydration condensation of plant-derived sebacic acid and plant-derived 1,3-propanediol. Furthermore, polybutylene succinate polyol can be obtained by direct dehydration condensation of plant-derived succinic acid and plant-derived 1,4-butanediol, and these may be used in combination.

The polyurethane prepolymer obtained from these plant-derived components is preferably contained in an amount of 10% by mass or more, and can be made to be contained in an amount of 40% by mass or more in terms of solid content in the entire polyurethane prepolymer.

(Other diol compounds)
Furthermore, in addition to the above polymer diol compounds, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- Low molecular weight diol compounds such as butanediol and 1,3-butanediol can be used alone or in combination of two or more.

When the organic diisocyanate compound and the polymeric diol compound are reacted, the equivalent ratio of isocyanate group to hydroxyl group (isocyanate index) is usually 1.2:1 to 3.0:1, more preferably is in the range of 1.3:1 to 2.0:1. If the above-mentioned isocyanate index is smaller than 1.2, the polyurethane polyurea resin tends to be flexible, and the blocking resistance etc. may be low when printing the ink composition. Concomitant use may be necessary.

(Reaction between organic diisocyanate compound and polymer diol)
A catalyst can be used during the reaction between the organic diisocyanate compound and the polymeric diol.
Among them, it is preferable to use organometallic compounds, and examples of such organometallic compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride, dibutyltin sulfide, tributyltin sulfide, and tributyltin oxide. , dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide , tributyltin trichloroacetate, and tin compounds such as tin 2-ethylhexanoate; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; and iron 2-ethylhexanoate. , iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, zirconium naphthenate, and the like. Among these, titanium compounds such as tetrabutyl titanate are preferred.
Tertiary amine compounds can also be used, such as triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU). can be used.

(Chain extension and/or terminal treatment reaction)
As the chain extender, known chain extenders used in polyurethane polyurea resins as binders for ink compositions can be used. For example, among polyamine compounds, ethylenediamine, propylene diamine, tetramethylene diamine, hexamethylene diamine aliphatic diamines such as isophorone diamine, cycloaliphatic diamines such as 4,4'-dicyclohexylmethane diamine, aromatic diamines such as tolylene diamine, aromatic aliphatic diamines such as xylene diamine, N-(2 -Diamines having hydroxyl groups such as -hydroxyethyl)ethylenediamine (aminoethylethanolamine), N-(2-hydroxyethyl)propylenediamine, N,N'-di(2-hydroxyethyl)ethylenediamine, ethylene glycol, propylene glycol, Examples include diol compounds such as 1,4-butanediol, neopentyl glycol, diethylene glycol, and triethylene glycol.
Furthermore, a polyamine compound such as diethylenetriamine or triethylenetetramine can be used in combination within a range where the polyurethane polyurea resin does not gel.

As a reaction terminator for introducing a primary amino group and a secondary amino group into the terminals of a polyurethane polyurea resin, examples of polyamine compounds include aliphatic diamines such as ethylenediamine, propylene diamine, tetramethylene diamine, and hexamethylene diamine, and isophorone. diamine, alicyclic diamines such as 4,4'-dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as tolylene diamine, aromatic aliphatic diamines such as xylene diamine, N Examples include diamines having a hydroxyl group such as -(2-hydroxyethyl)ethylenediamine (aminoethylethanolamine) and N-(2-hydroxyethyl)propylenediamine. Among these, polyamines having a primary amino group such as diethylenetriamine and triethylenetetratriamine are preferred.
Reaction terminators that introduce hydroxyl groups into polyurethane polyurea resins include alkanolamines such as monoethanolamine and diethanolamine, and those having hydroxyl groups such as N-(2-hydroxyethyl)ethylenediamine and N-(2-hydroxyethyl)propylenediamine. Examples include diamines. In addition, known reaction terminators such as monoamine compounds and monoalcohol compounds can be used. Specifically, monoalkylamines such as n-propylamine and n-butylamine, and dialkylamines such as di-n-butylamine can be used. and monoalcohols such as ethanol.

(Ketimination of chain extender and/or reaction terminator)
In the production method of the present invention, a ketimine compound obtained by ketimine-forming the above-mentioned polyamine compound as a chain extender and/or reaction terminator with an excess amount of a ketone compound is used, and the chain extender and/or reaction terminator is Polyurethane polyurea resin is produced using a terminator. In particular, it is preferable to employ isophoronediamine and/or N-(2-hydroxyethyl)ethylenediamine from among the chain extenders and reaction terminators mentioned above.
A polyamine compound ketiminated with a ketone compound has a structure in which the oxygen atom of the ketone compound is replaced by the nitrogen atom of the amino group of the polyamine compound. Moreover, as the ketone compound to be used, acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol are preferable.
In this ketimination reaction, it is preferable not to use any solvent other than the ketone compound. In the present invention, ketimination under solvent-free conditions is defined as not using any solvent other than the ketone compound. Note that a polar organic solvent may be blended instead of under solvent-free conditions as long as it does not inhibit the subsequent chain elongation reaction or the effect that the polyurethane polyurea resin has no odor.
The present invention is a method for producing a polyurethane polyurea resin, which includes a step of elongating the chain and terminating the reaction using a ketiminated chain extender and/or a reaction terminator, and the resulting polyurethane polyurea resin is Does not generate ketimine odor. In addition, when dissolved in an organic solvent to form an ink composition or the like, it exhibits an effect of excellent stability over time.
Note that it is more desirable to use a ketiminated amine or the like as a chain extender, and in this case, it is more preferable not to use a ketiminated compound as a terminal stopper.

(Synthesis of polyurethane polyurea resin from urethane prepolymer)
A polyurethane polyurea resin is obtained by subjecting the urethane prepolymer obtained by the above method to ketimine chain extension and/or reaction termination.
For this purpose, a solvent is added as necessary to the reaction product of the organic diisocyanate compound and the polymeric diol compound, and the above-mentioned ketiminated chain extender and/or reaction terminator is added to carry out the reaction. conduct.
The solvent at this time is preferably an ester solvent and/or an alcohol solvent, more preferably a mixture of an ester solvent and an alcohol solvent, and even more preferably propyl acetate and isopropyl alcohol. The most preferred range is from 1 to 5:1.

Further, when the obtained polyurethane polyurea resin has an amino group, it is preferable that the amine value is 1 to 10 mgKOH/g. If the amine value is less than 1 mgKOH/g, the adhesion to the film will decrease when used as a gravure ink composition for lamination, and the suitability for lamination may also decrease, and if the amine value is less than 10 mgKOH/g. If it exceeds g, blocking resistance may decrease.
In the present invention, the above-mentioned amine value means the amine value per 1 g of solid content, and is determined by potentiometric titration method (for example, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK) using a 0.1N hydrochloric acid aqueous solution. -900), manufactured by Hiranuma Sangyo Co., Ltd.) and converted to the equivalent amount of potassium hydroxide.

(Ink composition containing polyurethane polyurea resin)
The polyurethane resin obtained by the above manufacturing method is combined with a coloring agent that can be either a pigment or a dye, a solvent, a filler such as silica, a vinyl chloride/vinyl acetate copolymer, a vinyl chloride/acrylic copolymer, and a pigment dispersant. An ink composition is prepared by blending a dispersion aid, rosin and its derivatives, chlorinated polypropylene, dammar resin, polyethylene wax, fatty acid amide, etc.
Known methods can be used to produce an ink composition, particularly a gravure ink composition for lamination, using the necessary constituent materials. Specifically, for example, a mixture of a pigment, a binder resin, an organic solvent, and if necessary a pigment dispersant, etc. is ground using a high-speed mixer, a ball mill, a sand mill, an attritor, etc., and further, predetermined additives are added. It can be obtained by adding and mixing the rest of the materials.
Further, the paint containing the polyurethane polyurea resin obtained according to the present invention can also be obtained by known means for preparing paints. The components that can be used in the ink composition described below can also be used in the paint.

(Organic solvent)
There are no particular restrictions on the solvent that may be used in the ink composition containing the polyurethane polyurea resin obtained by the present invention, but from the viewpoint of environmental considerations, it is preferred not to contain aromatic hydrocarbon organic solvents. preferable. Examples of such solvents include alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate, ethyl acetate, propyl acetate, and butyl acetate. Ester organic solvents such as n-hexane, n-heptane, n-octane; alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, etc. Examples include solvents. At least one type of solvent may be used, and two or more types may be used in combination, taking into consideration the solubility and drying properties of the binder resin. However, from the viewpoint of being more considerate to the environment, it is preferable to suppress the use of ketone-based organic solvents among the above-mentioned solvents.
Furthermore, the ink composition containing the polyurethane polyurea resin obtained according to the present invention may contain 0.1 to 20% by weight of a glycol ether organic solvent based on 100% by weight of the organic solvent in order to improve wetting and spreading properties. is preferred. Specific examples of glycol ether organic solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and ethylene glycol. Examples include monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.
As a further preferred solvent, the solvent used in the chain extension and/or reaction termination step, as described above, can be employed. In this case, as mentioned above, a mixed solvent of an ester solvent and an alcohol solvent is preferable, and a mixed ester formed by mixing ethyl acetate and propyl acetate in a ratio of ethyl acetate:propyl acetate = 1 to 4:1 on a mass basis. More preferred is a solvent obtained by mixing a solvent and isopropyl alcohol in a ratio of mixed ester solvent: isopropyl alcohol = 1 to 5:1.
The ink composition containing the polyurethane polyurea resin obtained according to the present invention may contain water from the viewpoints of alleviating printing defects caused by static electricity, preventing plate fogging, and improving cell reproducibility. The amount of water used in the ink composition is preferably 10% by mass or less, and preferably in the range of 0.1 to 5.0% by mass.

(silica)
Examples of the silica that can be incorporated into the ink composition containing the polyurethane polyurea resin obtained according to the present invention include naturally occurring, synthetic, crystalline, non-crystalline, hydrophobic, and hydrophilic silica. The average particle size of the silica particles is preferably in the range of 1 to 5 μm (the average particle size of the silica particles means the particle size at 50% (D50) of the integrated value in the particle size distribution, and can be determined by the Coulter counter method. ). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or may be hydrophobic silica made hydrophobic by modifying the hydrophilic functional group with an alkylsilane or the like, but hydrophilic particles are preferred. The ink composition containing hydrophilic silica particles also has the effect of promoting wetting and spreading of the ink composition during overprinting and improving the overprinting effect (hereinafter sometimes referred to as "trapping property"). The amount of silica particles used in the gravure ink composition for lamination is 3.0% by mass or less, preferably 0.1 to 3.0% by mass, more preferably 0.2 to 1.5% by mass. When the content is more than 3.0% by mass, gloss tends to decrease.

(Vinyl chloride/vinyl acetate copolymer that can be blended into an ink composition containing the polyurethane polyurea resin obtained by the present invention)
The vinyl chloride/vinyl acetate copolymer contains vinyl chloride monomer and vinyl acetate monomer, which are conventionally used in gravure ink compositions, etc., as essential components, and if necessary, vinyl propionate, monochlorovinyl acetate, and versatile vinyl acetate. Fatty acid vinyl monomers such as vinyl acid, vinyl stearate, vinyl benzoate, etc., and monomers having functional groups such as hydroxyl groups produced by conventional methods can be used.
Among them, vinyl chloride/vinyl acetate copolymers have hydroxyl groups, preferably 50 to 200 hydroxyl groups, in organic solvent systems of environmentally friendly ink compositions. is suitable. Such a vinyl chloride/vinyl acetate copolymer having a hydroxyl group can be obtained by saponifying a part of the acetate ester moiety and introducing a (meth)acrylic monomer having a hydroxyl group.
In the case of a vinyl chloride/vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate ester moiety, a structural unit based on the reactive site of vinyl chloride in the molecule (formula 1 below), acetic acid The physical properties and dissolution behavior of the resin film are determined by the ratio of the structural unit based on the vinyl reaction site (formula 2 below) and the structural unit based on the saponification of the vinyl acetate reaction site (formula 3 below). In other words, the structural units based on the reactive sites of vinyl chloride impart toughness and hardness to the resin film, the structural units based on the reactive sites of vinyl acetate impart adhesiveness and flexibility, and the structural units based on the reactive sites of vinyl acetate impart saponification. The structural units based on the above provide good solubility of the environmentally friendly ink composition in organic solvent systems.
Formula 1 -CH ₂ -CHCl-
Formula 2 -CH ₂ -CH(OCOCH ₃ )-
Formula 3 -CH ₂ -CH(OH)-
Such vinyl chloride/vinyl acetate copolymers may be commercially available, such as Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, manufactured by Nissin Chemical Industry Co., Ltd. CNL etc. can be mentioned.
Note that the vinyl chloride/vinyl acetate copolymer used in the ink composition containing the polyurethane polyurea resin obtained by the present invention has various compounds in the molecule from the viewpoint of solubility in organic solvents and printability, which will be described later. Preferably, it has a functional group.
Further, when an environmentally friendly solvent is used as the organic solvent, it is preferable that the vinyl chloride/vinyl acetate copolymer has 50 to 200 hydroxyl groups. As commercial products of such vinyl chloride/vinyl acetate copolymers, it is preferable to use, for example, Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, etc. manufactured by Nissin Chemical Industries, Ltd.

(Vinyl chloride/acrylic copolymer that can be blended into an ink composition containing the polyurethane polyurea resin obtained by the present invention)
The main component is a copolymer of vinyl chloride and acrylic monomer. The form of the copolymer is not particularly limited; for example, the acrylic monomer may be incorporated block or randomly into the main chain of polyvinyl chloride, or may be graft copolymerized with the side chain of polyvinyl chloride. .
As the acrylic monomer, a (meth)acrylic acid ester, an acrylic monomer having a hydroxyl group, etc. can be used. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, and the alkyl group may be linear, branched, or cyclic, but a linear alkyl group is preferable. For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylic acid Examples include octadecyl.
Examples of acrylic monomers having hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; , polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycol mono(meth)acrylate such as 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone-modified (meth)acrylate, hydroxyethyl acrylamide, etc. Can be mentioned.
Moreover, as the acrylic monomer, an acrylic monomer having a functional group other than a hydroxyl group can also be used. Examples of functional groups other than hydroxyl groups include carboxyl groups, amide bonding groups, amino groups, and alkylene oxide groups.
The vinyl chloride/acrylic copolymer resin preferably has a mass weight average molecular weight of 10,000 to 70,000.
Further, from the viewpoint of solubility in an environmentally friendly organic solvent and adhesion to a substrate, the vinyl chloride/acrylic copolymer preferably has 50 to 200 hydroxyl groups.

As described above, the ink composition containing the polyurethane polyurea resin obtained according to the present invention may contain a vinyl chloride/vinyl acetate copolymer or /or a vinyl chloride/acrylic copolymer can be used in combination.
Polyurethane polyurea resin and (vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) are combined into polyurethane polyurea resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer). (polymer) = 100/0 to 45/55 (mass ratio). More preferably, this mass ratio may be set to 95/5 to 70/30. An ink composition containing a polyurethane polyurea resin obtained according to the present invention by containing a polyurethane polyurea resin and a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer in such proportions. will have even better printability and adhesion to the film. Furthermore, if lamination processing is performed, it will have better lamination suitability.
When the above polyurethane polyurea resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) is less than 45/55, (vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/ (acrylic copolymer) increases, the printed matter formed using the ink composition containing the polyurethane polyurea resin obtained by the present invention becomes hard, and there is also a possibility that the adhesion to the above film will be insufficient. be.

[Pigment dispersant that can be used in combination with the ink composition containing the polyurethane polyurea resin obtained by the present invention]
As the pigment dispersant that can be used in combination, polyester pigment dispersants that can be used in ink compositions such as gravure ink compositions that generally contain organic solvents can be used. Specifically, examples include Ajisper PB821, PB822, PB824, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Solspers 24000, 56000 (manufactured by Nippon Lubrizol Co., Ltd.), and among these, basic group-containing polyester polymer dispersants can be suitably used.
The content of the pigment dispersant is usually preferably 1 to 200 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of the total pigment.

(Other ingredients that can be used in combination)
The ink composition containing the polyurethane polyurea resin obtained by the present invention preferably contains at least one selected from rosin and its derivatives, dammar resin, chlorinated polypropylene, silica, polyethylene wax, and fatty acid amide. .
Rosin and its derivatives, Dammar resin, and chlorinated polypropylene improve adhesion to various films and suitability for lamination. It is preferable to contain one or more of these.
Silica, polyethylene wax, and fatty acid amide improve trapping properties and blocking resistance. It is preferable to contain one or more types of these, preferably two or more types.

(Rosin and its derivatives)
Examples of the rosin include gum rosin, tall oil rosin, and wood rosin. Generally, rosin is an amber-colored, amorphous resin obtained from pine, and because it is obtained from nature, it is a mixture, but it includes abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, The dehydroabietic acid component may be isolated and used, and in the present invention, these are also defined as rosin.
Rosin derivatives are compounds obtained by modifying the above-mentioned rosin, and are specifically listed below.
(1) Hydrogenated rosin: A rosin with improved weather resistance by adding hydrogen to conjugated double bonds (hydrogenation).
(2) Disproportionated rosin: Disproportionation means that two molecules of rosin react, and two molecules of abietic acid with a conjugated double bond form, one of which is aromatic and the other is a single double bond. It is a denaturation that becomes a bonding molecule. Weather resistance is generally inferior to hydrogenated rosin, but better than untreated rosin.
(3) Rosin-modified phenolic resin: Rosin-modified phenolic resin is often used as the main binder in offset printing ink compositions. Rosin-modified phenolic resin can be obtained by a known manufacturing method.
(4) Rosin ester: This is an ester resin derived from rosin, and has been used as a tackifier for adhesives and adhesives since ancient times.
(5) Rosin-modified maleic acid resin: A product obtained by addition-reacting maleic anhydride to rosin, and also includes a product obtained by esterifying and grafting a hydroxyl group-containing compound such as glycerin with an anhydride group as necessary.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosin and rosin derivatives can also be used, and these can be used not only alone but also in combination.
Furthermore, the acid value of rosin and rosin derivatives is preferably 120 mgKOH/g or more. When the acid value is 120 mgKOH/g or more, the laminate strength improves. More preferably, the acid value is 160 mgKOH/g or more. Further, the total amount of rosin and rosin derivative used is 3.0% by mass or less, preferably 0.1% by mass to 3% by mass of the solid content of the ink composition containing the polyurethane polyurea resin obtained by the present invention. .0% by mass.

(chlorinated polypropylene)
As the chlorinated polypropylene, those having a degree of chlorination of 20 to 50 can be used. Chlorinated polypropylene with a chlorination degree of less than 20 tends to have reduced compatibility with organic solvents. On the other hand, when the degree of chlorination exceeds 50, the adhesion of the chlorinated polypropylene to the film tends to decrease. Note that the degree of chlorination is defined as the mass % of chlorine atoms in the chlorinated polypropylene resin. Further, the chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene having a weight average molecular weight of 5,000 to 200,000. When the weight average molecular weight is less than 5000, the adhesiveness of chlorinated polypropylene tends to decrease. On the other hand, when the weight average molecular weight exceeds 200,000, the solubility of the chlorinated polypropylene in organic solvents tends to decrease. Further, the amount of chlorinated polypropylene used is 3.0% by mass or less, preferably 0.1% by mass to 3.0% by mass of the ink composition containing the polyurethane polyurea resin obtained by the present invention. Mass%.

(Dammar resin)
Dammar resin, also written as dammar or dammar, is a type of natural resin derived from plants. Specifically, it is a type of natural resin obtained from plants of the family Dipterocarpaceae or Orchidaceae that grow in Southeast Asia such as Malaysia and Indonesia. When used, it is dissolved in a suitable organic solvent to form a varnish. Since Dammar resin does not contain chlorine, chlorine can be eliminated and reduced compared to when a chlorinated polyolefin resin is used in the ink composition. Further, the amount of Dammar resin used is 3.0% by mass or less, preferably 0.1% by mass to 3.0% by mass in terms of solid content mass% of the ink composition containing the polyurethane polyurea resin obtained by the present invention. %.

(polyethylene wax)
The polyethylene wax used has an average particle size in the range of 1.0 to 3.0 μm (the average particle size means the particle size measured with #1 Microtrac UPA manufactured by Honeywell). If the particle size of the polyethylene wax is smaller than 1.0 μm, the slip properties and blocking properties will be reduced, and if the particle size is larger than 3.0 μm, the trapping property will be reduced. Further, the content of polyethylene wax in the ink composition containing the polyurethane polyurea resin obtained by the present invention is preferably 1.5% by mass or less, more preferably in the range of 0.1 to 1.5% by mass. use. When the content is more than 1.5% by mass, gloss tends to decrease.

(fatty acid amide)
The fatty acid amide is not particularly limited as long as it has a fatty acid residue and an amide group. Examples of fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, and esteramides, and at least one selected from the group consisting of monoamides, substituted amides, and bisamides because blocking resistance is improved. It is preferable. The amount of fatty acid amide used in the ink composition containing the polyurethane polyurea resin obtained by the present invention is 1% by mass or less, preferably in the range of 0.01 to 1% by mass.

- Monoamide: Monoamide is represented by the following general formula (1).
General formula (1) R1-CONH ₂
(In the formula, R1 represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide, and the like.
- Substituted amide: The substituted amide is represented by the following general formula (2).
General formula (2) R2-CONH-R3
(In the formula, R2 and R3 represent residues obtained by removing COOH from fatty acids, and may be the same or different.)
Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and the like.

- Bisamide: Bisamide is represented by the following general formula (3) or general formula (4).
General formula (3) R4-CONH-R5-HNCO-R6
General formula (4) R7-NHCO-R8-CONH-R9
(In the formula, R4, R6, R7, and R9 represent residues obtained by removing COOH from a fatty acid, and may be the same or different, and R5 and R8 represent an alkylene group or an arylene group having 1 to 10 carbon atoms. )
Specific examples of bisamides include methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bisstearic acid amide. , hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N,N'-distearyladipic acid amide, N,N'- Examples include distearyl sebacic acid amide, N,N'-dioleyl adipic acid amide, N,N'-dioleyl sebacic acid amide, and the like.

- Methylolamide: Methylolamide is represented by the following general formula (5).
General formula (5) R10-CONHCH ₂ OH
(In the formula, R10 represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of methylolamide include methylol palmitic acid amide, methylol stearic acid amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, methylol erucic acid amide, and the like.

- Esteramide: Esteramide is represented by the following general formula (6).
General formula (6) R11-CONH-R12-OCO-R13
(In the formula, R11 and R13 represent a residue obtained by removing COOH from a fatty acid, and may be the same or different, and R12 represents an alkylene group or an arylene group having 1 to 10 carbon atoms.)
Specific examples of esteramides include stearamide ethyl stearate, oleylamide ethyl ureate, and the like.
The melting point of the fatty acid amide is preferably 50°C to 150°C.
Further, as the fatty acid constituting the fatty acid amide, saturated fatty acids having 12 to 22 carbon atoms and/or unsaturated fatty acids having 16 to 25 carbon atoms are preferable, and saturated fatty acids having 16 to 18 carbon atoms and/or saturated fatty acids having 18 to 22 carbon atoms are preferable. More preferred are unsaturated fatty acids. Particularly preferred saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid, and particularly preferred unsaturated fatty acids are oleic acid and erucic acid.
Further, nitrified cotton, cellulose acetate propionate resin, and cellulose acetate butyrate resin can also be included in the ink composition for the purpose of improving blocking resistance.

(nitrified cotton)
As the nitrified cotton, nitrified cotton conventionally used in gravure ink compositions and the like can be used. Nitrified cotton is obtained as a nitric acid ester by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the six-membered ring of the anhydrous glucopyranose group in natural cellulose with nitric acid groups. The nitrified cotton used in the present invention preferably has a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90. Specific examples include SS1/2, SS1/4, SS1/8, TR1/16, NC RS-2, (KCNC, KOREA CNC LTD.
(manufactured by a company), etc. The amount of nitrified cotton used in the ink composition containing the polyurethane polyurea resin obtained by the present invention is preferably 2.0% by mass or less.

(cellulose acetate propionate resin)
As the cellulose acetate propionate resin, cellulose acetate propionate resin conventionally used in gravure ink compositions and the like can be used.
Cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid and then hydrolyzing it. Generally, commercially available resins contain 0.6 to 2.5% by weight of acetyl groups, 42 to 46% by weight of propionate groups, and 1.8 to 5% by weight of hydroxyl groups. The amount of cellulose acetate propionate resin used in the ink composition containing the polyurethane polyurea resin obtained by the present invention is preferably 3.0% by mass or less.

(cellulose acetate butyrate resin)
As the cellulose acetate butyrate resin, a cellulose acetate butyrate resin conventionally used in gravure ink compositions and the like can be used.
Cellulose acetate butyrate resin is obtained by triesterifying with acetic acid and butyric acid and then hydrolyzing the resin. Generally, commercially available resins contain 2 to 30% by weight of acetylation, 17 to 53% by weight of butyrylation, and 1 to 5% of hydroxyl groups. The amount of cellulose acetate butyrate resin used is preferably in the range of 0.1 to 3.0% by mass in the ink composition containing the polyurethane polyurea resin obtained by the present invention.

(Other various additives)
Various additives such as antistatic agents and plasticizers can be further added to the ink composition containing the polyurethane polyurea resin obtained by the present invention.

[Method for manufacturing laminated printed matter using ink composition using polyurethane polyurea resin obtained by the present invention]
Next, a method for obtaining laminated printed matter by using an ink composition using the polyurethane polyurea resin obtained according to the present invention as a gravure ink composition for lamination will be described. The polyurethane polyurea resin obtained by the present invention can also be used for purposes other than lamination and gravure.
The method for obtaining the laminated printed matter includes at least the following printing method. For example, a gravure ink composition for lamination is printed at least once or more by a gravure printing method on a resin film that is a known base material for lamination. Next, another gravure ink composition for lamination is printed using a gravure printing method on any part of the surface side (lower layer side when viewed from the surface layer after final lamination) of the gravure ink composition for lamination formed by these printings. and dry it with a hair dryer.
A laminated printed material for packaging bags and the like can be obtained by laminating a resin film or the like by various methods on the side of the layer of the laminating gravure ink composition of the printed material obtained by the above method. This laminating method includes the extrusion lamination method, in which an anchor coating agent is applied to the surface of the printed material and then a molten polymer is laminated thereon, and the dry method, in which a film-like polymer is laminated after the surface of the printed material is coated with an adhesive. Lamination method can be used.

In the extrusion lamination method, after applying an anchor coating agent such as a titanium-based, urethane-based, imine-based, or polybutadiene-based anchor coating agent to the surface of the printed matter containing a layer of a gravure ink composition for lamination, if necessary, This is a method in which molten polymers are laminated using an extrusion laminating machine, and the molten resin can also be used as an intermediate layer to laminate other materials in the form of a sandwich.
As the molten polymer used in the extrusion lamination method, conventionally used resins such as low density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc. can be used. Among them, the effects of the present invention will be enhanced if low-density polyethylene, which is easily oxidized to generate carbonyl groups during melting, is used.

The dry lamination method described above is a method in which a urethane-based or isocyanate-based adhesive is applied to the surface of a layer made of a gravure ink composition for lamination, and then a film-like polymer is laminated using a known dry lamination machine. be. As the resin for the film used in the dry lamination method, polyethylene, unstretched polypropylene, etc. can be used. In particular, in order to obtain a packaging material used for retort applications, aluminum foil may be sandwiched between the base material and the resin film to be laminated. Such laminated products can also be used for boiling and retort applications after being made into bags and filled with contents.
Examples of the resin film used at this time include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon. Furthermore, regarding these resin films, it is also possible to use films obtained by processing the resin film in advance, such as coating or kneading an antifogging agent, or surface coating or kneading a matting agent.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." In addition, the numbers for the quantities of each material in the table are also "parts by mass." The unit of acid value is mgKOH/g.

<Method for producing ketimine solution 1>
51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 174 parts of acetone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 1.
<Method for producing ketimine solution 2>
51 parts of isophorone diamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 258 parts of diethyl ketone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 2.
<Method for producing ketimine solution 3>
51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 210 parts of methyl ethyl ketone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 3.
<Method for producing ketimine solution 4>
51 parts of isophorone diamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 348 parts of diacetone alcohol were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 4.

<Production method of PU-1 (ketimine with acetone)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, after adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, it was cooled to near room temperature, and 25.6 parts of ketimine solution 1 was added and stirred for 30 minutes to obtain PU-1 (solid content 30% by mass). .

<Production method of PU-2 (ketimine formation with diethyl ketone)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, after adding 803 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, and 34 parts of ketimine solution 2 was added and stirred for 30 minutes to obtain PU-2 (solid content 30% by mass).

<Production method of PU-3 (ketimine formation with methyl ethyl ketone)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, after adding 807 parts of propyl acetate and 202 parts of isopropyl alcohol, it was cooled to near room temperature, and 29.2 parts of ketimine solution 3 was added and stirred for 30 minutes to obtain PU-3 (solid content 30% by mass). .

<Production method of PU-4 (ketimine formation with diacetone alcohol)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, after adding 796 parts of propyl acetate and 199 parts of isopropyl alcohol, the mixture was cooled to near room temperature, and 43 parts of ketimine solution 4 was added and stirred for 30 minutes to obtain PU-4 (solid content 30% by mass).

<Production method of PU-5 (adding acetone after chain extension and terminal termination with diamine)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, 810 parts of propyl acetate and 202 parts of isopropyl alcohol were added, then cooled to near room temperature, 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added, and the mixture was stirred for 30 minutes. , 17.4 parts of acetone was added and stirred for 30 minutes to obtain PU-5 (solid content 30% by mass).

<Production method of PU-6 (adding diethyl ketone after chain extension and terminal termination with diamine)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, 803 parts of propyl acetate and 201 parts of isopropyl alcohol were added, then cooled to near room temperature, 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added, and the mixture was stirred for 30 minutes. , 25.8 parts of diethyl ketone were added and stirred for 30 minutes to obtain PU-6 (solid content 30% by mass).

<Production method of PU-7 (adding methyl ethyl ketone after chain extension and terminal termination with diamine)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, 807 parts of propyl acetate and 202 parts of isopropyl alcohol were added, then cooled to near room temperature, 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added, and the mixture was stirred for 30 minutes. , 21 parts of methyl ethyl ketone were added and stirred for 30 minutes to obtain PU-7 (solid content 30% by mass).

<Production method of PU-8 (adding diacetone alcohol after chain extension and terminal termination with diamine)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0 parts of tetrabutyl titanate were added. 0.04 parts were charged and reacted at 90 to 100°C for 6 hours while introducing nitrogen gas.
Next, after adding 796 parts of propyl acetate and 199 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added, and the mixture was stirred for 30 minutes. , 34.8 parts of diacetone alcohol was added and stirred for 30 minutes to obtain PU-8 (solid content 30% by mass).

(pigment)
Titanium oxide (R-960, manufactured by DuPont)
Phthalocyanine blue (pigment blue 15:4)
<Silica particles>
Silica particles with an average particle diameter of 4.5 μm

<Manufacture examples of each ink composition of Examples and Comparative Examples>
Pigments, polyurethane resin varnishes (PU-1 to PU-8), silica, and solvent were kneaded using a paint conditioner manufactured by Red Devil Co., Ltd. to obtain ink compositions of Examples and Comparative Examples shown in Table 1.

<Stability of ink composition over time>
The ink compositions of Examples and Comparative Examples obtained above were collected in a glass bottle, and after storage at 60°C for 30 days, the stability over time of the ink compositions was evaluated based on the following evaluation criteria based on the presence or absence of pigment sedimentation by visual observation. Therefore, it was evaluated. The results are shown in Table 1.
○: No sedimentation observed.
△: Sedimentation is observed, but it is recovered by shaking.
×: Sedimentation is observed and does not recover even by shaking.

<Manufacture of printed matter>
100 parts by mass of each of the ink compositions of Examples and Comparative Examples was diluted with a mixed solvent (ethyl acetate/propyl acetate/isopropyl alcohol = 50/25/25, mass ratio), and the viscosity was measured using Zahn Cup 3 manufactured by Rigosha. The concentration was adjusted to 15 seconds to obtain an ink composition.
Each of the obtained ink compositions was used to print and dry the treated surface of a polypropylene film (P-2161 manufactured by Toyobo Co., Ltd.) under the following conditions to obtain printed matter.
Furthermore, the obtained printed matter was evaluated for ketimine odor. The specific evaluation method is shown below.

(Printing method/printing conditions)
Room environment during printing: temperature 25℃, humidity 50%
Coating machine: Gravure printing machine
Coating speed: 150m/min
Printing plate: Direct 175 line 28μm solid plate Drying temperature: 55℃

(Ketimine odor evaluation method for printed matter)
The nose was placed on the printed surface of each of the obtained printed materials, and the odor was evaluated using a sensory test according to the following criteria. The results are shown in Table 1.
○: Ketimine odor is not observed.
Δ: Slight ketimine odor is observed.
×: Ketimine odor is observed.

The ink compositions of Examples 1 to 5 using the polyurethane polyurea resin obtained by the method of the present invention had excellent stability over time as an ink composition. In addition, there was no ketimine odor in the printed area after printing.
On the other hand, the ink compositions of Comparative Examples 1 to 5, which used polyurethane polyurea resins that were not ketiminated, had poor stability over time as ink compositions. In addition, there was a ketimine odor in the printed area after printing.

Claims (3)

Synthesize urethane prepolymer from diol compound and diisocyanate compound,
Next, the urethane prepolymer is reacted with a chain extender and/or a reaction terminator in which the amino group of a polyamine compound has been ketiminated with a ketone compound under a solvent-free condition in a polar organic solvent under stirring ,
A method for producing a polyurethane polyurea resin with ketimine terminals. The chain extender and/or reaction terminator is a chain extender and/or reaction terminator that has been ketiminated with one or more types selected from acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol as the ketone compound . Item 1. A method for producing a polyurethane polyurea resin having a ketiminated terminal as described in Item 1. The method for producing a polyurethane polyurea resin with a ketiminated terminal according to claim 1 or 2 , wherein only the chain extender is ketiminated.