JP2021066824A - Method for producing polyurethane resin - Google Patents

Abstract

To provide a method for producing a polyurethane polyurea resin that solves the problems of a residual odor of a polyurethane polyurea resin composition with a terminal amino group ketiminized as well as reduced stability with time.SOLUTION: According to a method herein, a urethane prepolymer is synthesized from a diol compound and a diisocyanate compound, and then, the urethane prepolymer is caused to react with a chain extender and/or reaction stop agent in which an amino group of a polyamine compound is ketiminized with a ketone compound under a solvent-free condition, in a polar organic solvent, resulting in a polyurethane polyurea resin with a ketiminized terminal.SELECTED DRAWING: None

Description

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

As described in Patent Document 1, it is known that chain extension and reaction termination are carried out with respect to urethane prepolymer, and then a ketone compound is reacted with an amino group at the terminal of the obtained polyurethane resin to carry out ketimification. There is. According to such a method for synthesizing a ketiminated polyurethane resin, it is said that the odor is reduced and the viscosity stability is excellent.
According to this synthetic method, even if the pungent odor caused by acetone is reduced, the low molecular weight chain extender and reaction terminator existing in the system are also ketiminated.
In the end, the odor of the composition as a whole could not be sufficiently suppressed because another odor caused by the ketiminated low molecular weight chain extender and reaction terminator was generated.
Further, the effect on viscosity stability is a result of suppressing the reduction of the molecular weight of polyurethane during storage, but the ink composition is provided by the ketiminated low molecular weight chain extender and reaction terminator that cannot be completely removed and remain. There was a problem that the stability over time was reduced when it was used as a paint or paint.

Further, as described in Patent Documents 2 and 3, it is known that a polyurethane polyurea resin powder for slush molding or the like can be obtained by reacting a ketimine compound obtained from a diamine and a ketone with a urethane prepolymer under an aqueous solvent. Has been done.
Further, in particular, Patent Document 2 describes that a urethane prepolymer is chain-extended with a bimolecular condensate of a ketone in the presence of water and a dispersion stabilizer.

Japanese Unexamined Patent Publication No. 2017-2184 Japanese Unexamined Patent Publication No. 2012-251010 Japanese Unexamined Patent Publication No. 2011-208128

An object to be solved by the present invention is to eliminate the residual odor and the decrease in stability over time contained in the polyurethane polyurea resin composition in which the terminal amino group is ketiminated.

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

According to the present invention, it is possible to exhibit the effect that the ink composition and the printed matter do not have the odor peculiar to ketimine, and that the ink composition is excellent in stability over time.

The production method of the present invention employs a ketimine compound obtained under specific conditions as a chain extender and / or a reaction terminator, and reacts with a urethane prepolymer in a specific solvent to obtain the polyurethane polyurea resin itself. However, it does not generate the odor of ketimine, and is excellent in stability over time when stored in a solution state of an ink composition or paint.
Hereinafter, a method for producing the polyurethane polyurea resin of the present invention will be described.

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

<Synthesis of urethane prepolymer>
The urethane prepolymer is obtained by reacting the following organic diisocyanate compound with a high molecular weight diol compound.
(Organic diisocyanate compound)
Examples of the organic diisocyanate compound include 1,3- and / or 1,4-phenylenediocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, and tolylene diisocyanate. Aromatic diisocyanate compounds, dicyclohexylmethane 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexamethylene 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 alone or in combination of two or more. Can be mixed and used. Of these, alicyclic diisocyanates, aliphatic diisocyanates and aromatic aliphatic diisocyanates are more preferable.

(Polymer diol compound)
Examples of the high molecular weight diol compound include one or more dibasic acids such as adipic acid, sebacic acid, and futalic anhydride, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 3 Polyesterdiols obtained by condensing one or more of glycols such as -methyl-1,5-pentanediol, polyesterdiol compounds such as polycaprolactone diols, polyethylene glycol, polypropylene glycol and the like. Polyalkylene glycols, ethylene oxide of bisphenol A, polyether diol compounds such as alkylene oxide adducts such as propylene oxide, and the like can be mentioned. These high molecular weight diol compounds can be used alone or in combination of two or more. Of these, 3-methyl-1,5-pentylene adipatediol having a number average molecular weight of 1000 to 8000 obtained by condensation reaction of adipic acid and 3-methyl-1,5-pentanediol is preferable, and further, the number average molecular weight is more preferable. 1000-4000 3-methyl-1,5-pentylene adipatediols are preferred.

(Biopolyesterdiol compound)
In consideration of the environment, the biopolyester diol compound may be synthesized from a material containing a plant-derived component.
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 a plant 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 adopted. As the biopolyol component, it is more preferable that at least one of the short-chain diol compound and the carboxylic acid component is derived from a plant, and it is further preferable that both are derived from a plant.
The plant-derived short-chain diol compound having 2 to 4 carbon atoms is not particularly limited. As an example, the short chain diol compound may be 1,3-propanediol, 1,4-butanediol, ethylene glycol or the like obtained from a plant raw material by the following method. These may be used together.
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 (for example, corn). The 1,3-propanediol compound produced by a bio method such as the above fermentation method can obtain useful by-products such as lactic acid as compared with the 1,3-propanediol compound produced by the EO production method, and is also produced. The cost can also be kept low. 1,4-Butanediol can be produced by obtaining succinic acid obtained by producing glycol from plant resources and fermenting it, and hydrogenating it. Further, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

The plant-derived carboxylic acid is not particularly limited. For example, the carboxylic acid is sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid and the like. These may be used together. Among these, the carboxylic acid component preferably 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 with respect to 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, a polytrimethylene sebacate polyol can be obtained by directly dehydrating and condensing plant-derived sebacic acid and plant-derived 1,3-propanediol. Further, a polybutylene succinate polyol can be obtained by directly dehydrating and condensing 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 in terms of solid content, and can be contained in an amount of 40% by mass or more in the total polyurethane prepolymer.

(Other diol compounds)
Further, in addition to the above high molecular weight diol compound, 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 reacting the organic diisocyanate compound with the polymer diol compound, the equivalent ratio of isocyanate group: hydroxyl group (isocyanate index) is usually 1.2: 1 to 3.0: 1, more preferably 1.2: 1 to 3.0: 1. Is in the range of 1.3: 1 to 2.0: 1. When the above isocyanate index is smaller than 1.2, it tends to be a flexible polyurethane polyurea resin, and the blocking resistance and the like may be low when the ink composition is printed. In this case, it is different from other hard resins. It may be necessary to use them together.

(Reaction between organic diisocyanate compound and high molecular weight diol)
A catalyst can be used during the reaction of the organic diisocyanate compound with the high molecular weight diol.
Of these, it is preferable to use an organic metal compound, and as such an organic metal compound, titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride, dibutyltin sulfide, tributyltin sulfide, and tributyltin oxide. , Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide. , Tin compounds such as tributyltin trichloroacetate and 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 preferable.
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 end 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, propylenediamine, tetramethylenediamine, and hexamethylenediamine can be used. Other aliphatic diamines, isophorone diamines, alicyclic diamines such as 4,4'-dicyclohexylmethanediamine, aromatic diamines such as toluylene 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 thereof include diol compounds such as 1,4-butanediol, neopentyl glycol, diamine glycol and triethylene glycol.
Further, a polyamine compound such as diethylenetriamine or triethylenetetramine can be used in combination as long as the polyurethane polyurea resin does not gel.

Examples of the reaction terminator for introducing a primary amino group and a secondary amino group into the terminal of the polyurethane polyurea resin include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine, and isophorone as polyamine compounds. Diamines, alicyclic diamines such as 4,4'-dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylene diamine, aromatic aliphatic diamines such as xylenediamine, N Examples thereof 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 preferable.
Examples of the reaction terminator for introducing a hydroxyl group into the polyurethane polyurea resin include alkanolamines such as monoethanolamine and diethanolamine, and hydroxyl groups such as N- (2-hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine. Diamines can be exemplified. Further, 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. Kind, monoalcohols such as ethanol can be exemplified.

(Ketimification of chain extender and / or reaction terminator)
In the production method of the present invention, a ketimine compound obtained by preliminarily ketiminizing a polyamine compound which is a chain extender and / or a reaction terminator with an excess amount of a ketone compound is used, and the chain extender and / or reaction thereof is used. Polyurethane polyurea resin is produced using a terminator. In particular, it is preferable to use isophoronediamine and / or N- (2-hydroxyethyl) ethylenediamine from the above chain extenders and reaction terminators.
The polyamine compound ketiminated by the 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. Further, as the ketone compound to be used, acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol are preferable.
It is preferable not to use a solvent other than the ketone compound in this ketimification reaction. In the present invention, the absence of a solvent other than a ketone compound is defined as ketimination under solvent-free conditions. A polar organic solvent may be blended instead of the solvent-free condition as long as the subsequent chain extension reaction and the effect that the polyurethane polyurea resin does not have an odor are not impaired.
The present invention is a method for producing a polyurethane polyurea resin which undergoes a step of causing chain elongation and reaction termination using a ketiminated chain extender and / or reaction terminator, and the resulting polyurethane polyurea resin is Does not generate a ketimine odor. In addition, it exhibits an effect of excellent stability over time when dissolved in an organic solvent to form an ink composition or the like.
It is more desirable to use a ketiminated amine or the like as a chain extender, and at that time, it is more preferable not to use a compound obtained by ketimination as a terminal terminator.

(Synthesis of polyurethane polyurea resin from urethane prepolymer)
A polyurethane polyurea resin is obtained by carrying out a reaction of ketiminated chain extension and / or reaction termination with respect to the urethane prepolymer obtained by the above method.
Therefore, if necessary, a solvent is added to the reaction product of the organic diisocyanate compound and the polymer diol compound, and further, the ketiminated chain extender and / or the reaction terminator is added to carry out the reaction. Do.
As the solvent at this time, an ester solvent and / or an alcohol solvent is preferable, a mixture of the ester solvent and the alcohol solvent is more preferable, propyl acetate and isopropyl alcohol are more preferable, and propyl acetate: isopropyl alcohol by mass ratio. The range of = 1 to 5: 1 is most preferable.

When the obtained polyurethane polyurea resin has an amino group, the amine value is preferably 1 to 10 mgKOH / g. If the amine value is less than 1 mgKOH / g, the adhesiveness to the film may be lowered, and the laminating suitability may be further lowered, for example, when the gravure ink composition for laminating is prepared, and the amine value is 10 mgKOH / g. If it exceeds g, the blocking resistance may decrease.
In the present invention, the amine value means the amine value per 1 g of solid content, and a potential difference titration method (for example, COMITE (AUTO TITTOROR COM-900, BURET B-900, TITSTATIONK) is used using a 0.1 N hydrochloric acid aqueous solution. -900), a value converted to the equivalent of potassium hydroxide after measurement by Hiranuma Sangyo Co., Ltd.).

(Ink composition containing polyurethane polyurea resin)
To the polyurethane resin obtained by the above production method, a colorant which may 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, a pigment dispersant And dispersion aids, rosin and its derivatives, chlorinated polypropylene, dammar resin, polyethylene wax, fatty acid amide, etc. are blended to prepare an ink composition.
A known method can be used as a method for producing an ink composition, particularly a gravure ink composition for laminating, using necessary constituent materials. Specifically, for example, a mixture of a pigment, a binder resin, an organic solvent and, if necessary, a pigment dispersant is kneaded using a high-speed mixer, a ball mill, a sand mill, an attritor or the like, and further, a predetermined additive is added. It can be obtained by adding and mixing the rest of the materials such as.
Further, the paint containing the polyurethane polyurea resin obtained by the present invention can also be obtained by a known means for preparing the paint. The components that can be used in the following ink compositions can also be used in the paint.

(Organic solvent)
The solvent that may be used in the ink composition containing the polyurethane polyurea resin obtained by the present invention is not particularly limited, but from the viewpoint of environmental consideration, it may not contain an aromatic hydrocarbon-based organic solvent. preferable. Examples of such a solvent 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-based organic solvents such as; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, n-octane; alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptan, cyclooctane, etc. Examples include solvents. At least one type of the solvent may be used, and two or more types may be used in combination in consideration of the solubility and drying property of the binder resin. However, from the viewpoint of considering the environment, it is preferable to suppress the use of ketone-based organic solvents among the above-mentioned solvents.
Further, the ink composition containing the polyurethane polyurea resin obtained by the present invention contains 0.1 to 20% by weight of a glycol ether-based organic solvent in 100% by weight of the organic solvent in order to improve the wettability. Is preferable. Specific examples of glycol ether-based 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 thereof include monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monon-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.
As a more preferable solvent, as described above, the solvent used in the chain extension and / or reaction termination step can be adopted. Also in this case, as described above, a mixed solvent of an ester solvent and an alcohol solvent is preferable, and a mixed ester composed of ethyl acetate and propyl acetate mixed in a mass-based manner of ethyl acetate: propyl acetate = 1 to 4: 1. A solvent obtained by mixing the system solvent and isopropyl alcohol in a mixed ester solvent: isopropyl alcohol = 1 to 5: 1 is more preferable.
The ink composition containing the polyurethane polyurea resin obtained by the present invention may contain water from the viewpoints of alleviating printing defects due to static electricity, preventing plate fog, and cell reproducibility. The amount of water used is preferably in the range of 10% by mass or less and 0.1 to 5.0% by mass in the ink composition.

(silica)
Examples of silica that can be blended in the ink composition containing the polyurethane polyurea resin obtained by the present invention include natural products, synthetic products, crystalline, non-crystalline, hydrophobic, and hydrophilic ones. The silica particles preferably have an average particle size in the range of 1 to 5 μm (the average particle size of the silica particles means the particle size at an integrated value of 50% (D50) in the particle size distribution, and is determined by the Coulter counter method. Can be done). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with alkylsilane or the like to make it hydrophobic, but hydrophilic particles are preferable. The ink composition containing hydrophilic silica particles also has an effect of promoting wetting and spreading of the ink composition during overlay printing and improving the overlay printing effect (hereinafter, may be referred to as “trapping property”). The amount of silica particles used is 3.0% by mass or less, preferably 0.1 to 3.0% by mass, and more preferably 0.2 to 1.5% by mass in the gravure ink composition for lamination. If the content is more than 3.0% by mass, the gloss tends to decrease.

(Vinyl chloride / vinyl acetate copolymer that can be blended in an ink composition containing a polyurethane polyurea resin obtained by the present invention)
The vinyl chloride / vinyl acetate-based copolymer contains vinyl chloride monomer and vinyl acetate monomer conventionally used in gravure ink compositions and the like as essential components, and vinyl propionate, monochloroacetate, and versatic as needed. A vinyl acetate monomer such as vinyl acetate, vinyl laurate, vinyl stearate, vinyl benzoate, or a monomer having a functional group such as a hydroxyl group produced by a conventionally known method can be used.
Among them, the vinyl chloride / vinyl acetate-based copolymer is a vinyl chloride / vinyl acetate-based copolymer having a hydroxyl group, preferably 50 to 200 hydroxyl groups in the organic solvent system of the environmentally friendly ink composition. Is preferable. Such a vinyl chloride / vinyl acetate-based 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-based copolymer having a hydroxyl group obtained by saponifying a part of the acetic acid ester moiety, a structural unit based on the reaction 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 reaction site of vinyl (formula 2 below) and the structural unit based on the saponification of the reaction site of vinyl acetate (formula 3 below). That is, the structural unit based on the reaction site of vinyl chloride imparts the toughness and hardness of the resin film, and the structural unit based on the reaction site of vinyl acetate imparts adhesiveness and flexibility, and the reaction site of vinyl acetate is saponified. The structural unit based on provides good solubility of environmentally friendly ink compositions in organic solvent systems.
Equation 1-CH _2- CHCl-
Equation 2-CH _2- CH (OCOCH ₃ )-
Equation 3-CH _2- CH (OH)-
Such a vinyl chloride / vinyl acetate-based copolymer may be commercially available, and for example, Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, manufactured by Nissin Chemical Industry Co., Ltd. CNL and the like can be mentioned.
The vinyl chloride / vinyl acetate copolymer used in the ink composition containing the polyurethane polyurea resin obtained by the present invention has various intramolecular components from the viewpoint of solubility in organic solvents and printability described later. It preferably has a functional group.
When an environment-friendly solvent is used as the organic solvent, the vinyl chloride / vinyl acetate copolymer preferably has 50 to 200 hydroxyl groups. As a commercially available product of such a vinyl chloride / vinyl acetate copolymer, for example, it is preferable to use solvene A, AL, TA5R, TA2, TA3, TAO, TAOL or the like manufactured by Nissin Chemical Industry Co., Ltd.

(Vinyl chloride / acrylic copolymer that can be blended in an ink composition containing a polyurethane polyurea resin obtained by the present invention)
The main component is a copolymer of vinyl chloride and an acrylic monomer. The form of the copolymer is not particularly limited, and for example, the acrylic monomer may be blocked or randomly incorporated in the main chain of polyvinyl chloride, or may be graft-copolymerized in the side chain of polyvinyl chloride. ..
As the acrylic monomer, a (meth) acrylic acid ester, an acrylic monomer having a hydroxyl group, or the like can be used. Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester, 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. , (Meta) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl acrylate, (meth) hexadecyl acrylate, (meth) acrylate Octadecyl and the like can be mentioned.
Examples of acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meta) Acrylic Acid Hydroxyalkyl esters such as (meth) Acrylic Acid 3-Hydroxybutyl, (Meta) Acrylic Acid 4-Hydroxybutyl, (Meta) Acrylic Acid 6-Hydroxyhexyl, (Meta) Acrylic Acid 8-Hydroxyoctyl , 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.
Further, as the acrylic monomer, an acrylic monomer having a functional group other than a hydroxyl group can also be used. Examples of the functional group other than the hydroxyl group include a carboxyl group, an amide bond group, an amino group, an alkylene oxide group and the like.
The vinyl chloride / acrylic copolymer resin preferably has a mass-weight average molecular weight of 10,000 to 70,000.
Further, the vinyl chloride / acrylic copolymer preferably has 50 to 200 hydroxyl groups from the viewpoint of solubility in an environment-friendly solvent as the organic solvent and adhesiveness to a base material.

As described above, in the ink composition containing the polyurethane polyurea resin obtained by the present invention, a vinyl chloride / vinyl acetate-based copolymer and a vinyl chloride / vinyl acetate-based copolymer are added to the polyurethane polyurea resin in order to improve the adhesion depending on the pigment to be blended. / Or a vinyl chloride / acrylic copolymer can be used in combination.
Polyurethane polyvinyl chloride resin and (vinyl chloride / vinyl acetate-based copolymer and / or vinyl chloride / acrylic copolymer), polyurethane polyvinyl chloride resin / (vinyl chloride / vinyl acetate-based copolymer and / or vinyl chloride / acrylic) Polymer) = 100/0 to 45/55 (mass ratio). More preferably, this mass ratio may be 95/5 to 70/30. An ink composition containing the polyurethane polyurea resin obtained by the present invention by containing the polyurethane polyurea resin and the vinyl chloride / vinyl acetate copolymer and / or the vinyl chloride / acrylic copolymer in such a ratio. Will have even better printability and adhesiveness to the film. Further, when the laminating process is performed, it will have better laminating suitability.
When the polyurethane polyurea resin / (vinyl chloride / vinyl acetate-based copolymer and / or vinyl chloride / acrylic copolymer) is less than 45/55, (vinyl chloride / vinyl acetate-based copolymer and / or vinyl chloride / The proportion of the acrylic copolymer) increases, and the printed matter formed by using the ink composition containing the polyurethane polyurea resin obtained by the present invention becomes hard, and the adhesiveness to the film may be insufficient. is there.

[Pigment Dispersant that can be used in combination with an ink composition containing a polyurethane polyurea resin obtained by the present invention]
As the pigment dispersant that can be used in combination, a polyester pigment dispersant that can be generally used for ink compositions such as gravure ink compositions containing an organic solvent can be used. Specific examples thereof include azisper PB821, PB822, PB824, PB881 (manufactured by Ajinomoto Fine-Techno), Solsperse 24000, 56000 (manufactured by Japan Lubrizol), and among these, a polyester polymer dispersant containing a basic group. Can be preferably used.
The content of the pigment dispersant is usually preferably 1 to 200 parts by mass, and more preferably 1 to 60 parts by mass with respect to 100 parts by mass of the total pigment.

(Other ingredients that can be used together)
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 the adhesiveness to various films and the suitability for laminating. It is preferable to contain one or more of these.
Silica, polyethylene wax, and fatty acid amide improve trapping resistance and blocking resistance. It is preferable to contain one or more of these, preferably two or more.

(Rosin and its derivatives)
Examples of the rosin include gum rosin, tall oil rosin, wood rosin and the like. Generally, rosin is an amber, amorphous resin obtained from pine and is a mixture because it is obtained from nature, but abietic acid, neoavietic acid, palastolic acid, pimalic acid, isopimalic acid, sandaracopimalic acid, Dehydroabietic acid may be isolated and used for each component, and these are also defined as rosins in the present invention.
The rosin derivative is a compound obtained by modifying the above rosin, and is specifically listed below.
(1) Hydrogenated rosin: A rosin having improved weather resistance by adding (hydrogenating) hydrogen to a conjugated double bond.
(2) Disproportionated rosin: Disproportionation is a reaction of two molecules of rosin, two molecules of abietic acid having a conjugated double bond, one of which constitutes an aromatic and the other of which is a single double. It is a modification that becomes a molecule of binding. It is generally less weather resistant than hydrogenated rosin, but better than untreated.
(3) Rosin-modified phenol resin: A rosin-modified phenol resin is often used as the main binder in the ink composition for offset printing. The rosin-modified phenol resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, which has been used as a tackifier (tack fire) for adhesives and adhesives for a long time.
(5) Rosin-modified maleic acid resin: A rosin to which maleic anhydride is added and reacted, and if necessary, a hydroxyl group-containing compound such as glycerin is esterified with no hydroxyl group and grafted.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosins and rosin derivatives can also be used, and these can be used not only alone but also in combination.
Further, 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 is improved. More preferably, the acid value is 160 mgKOH / g or more. The total amount of rosin and rosin derivative used is 3.0% by mass or less, preferably 0.1% by mass to 3%, based on the solid content mass% of the polyurethane polyurea resin obtained by the present invention. It is 0.0% by mass.

(Chlorinated polypropylene)
As the chlorinated polypropylene, polypropylene having a degree of chlorination of 20 to 50 can be used. Chlorinated polypropylene having a degree of chlorination of less than 20 tends to have low compatibility with an organic solvent. On the other hand, when the degree of chlorination exceeds 50, the chlorinated polypropylene tends to have a reduced adhesiveness to the film. The degree of chlorination is defined by 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 5000 to 20000. When the weight average molecular weight is less than 5000, the chlorinated polypropylene tends to have reduced adhesiveness. On the other hand, when the weight average molecular weight exceeds 200,000, the chlorinated polypropylene tends to have a reduced solubility in an organic solvent. The amount of chlorinated polypropylene used is 3.0% by mass or less, preferably 0.1% by mass to 3.0%, based on the solid content mass% of the ink composition containing the polyurethane polyurea resin obtained by the present invention. It is mass%.

(Dammal resin)
Dammar resin, also referred to as damar or dammer, is a type of plant-derived natural resin. Specifically, it is a kind of natural resin obtained from plants of the family Dipterocarpaceae or Torchwoodaceae growing in Southeast Asia such as Malaysia and Indonesia. When using it, dissolve it in a suitable organic solvent to make a varnish. Since the dammar resin does not contain chlorine, chlorine can be eliminated or reduced as compared with the case where a chlorinated polyolefin resin is used in the ink composition. The amount of the dammar resin used is 3.0% by mass or less, preferably 0.1% by mass to 3.0% by mass, based on the solid content mass% of the ink composition containing the polyurethane polyurea resin obtained by the present invention. %.

(Polyethylene wax)
As the polyethylene wax, one having an average particle size in the range of 1.0 to 3.0 μm (the average particle size means the particle size measured by Microtrac UPA manufactured by Honeywell Co., Ltd.) is used. If the particle size of the polyethylene wax is smaller than 1.0 μm, the slipperiness and blocking property are lowered, and if the particle size is larger than 3.0 μm, the trapping property is lowered. The content of polyethylene wax in the ink composition containing the polyurethane polyurea resin obtained by the present invention is preferably in the range of 1.5% by mass or less, more preferably 0.1 to 1.5% by mass. use. If the content is more than 1.5% by mass, the 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 the fatty acid amide include monoamide, substituted amide, bisamide, methylolamide, and ester amide, and are at least one selected from the group consisting of monoamide, substituted amide, and bisamide in order to improve blocking resistance. Is preferable. The amount of the fatty acid amide used is in the range of 1% by mass or less, preferably 0.01 to 1% by mass, in the ink composition containing the polyurethane polyurea resin obtained by the present invention.

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 fatty acid.)
Specific examples of the monoamide include lauric acid amide, palmitate amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, oleic acid amide, and erucic acid amide.
-Substitution amide: The substitution 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 the substituted amide include N-oleyl palmitate amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucate 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 fatty acids, and may be the same or different, and R5 and R8 represent alkylene groups or arylene groups having 1 to 10 carbon atoms. )
Specific examples of bisamides include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, and hexamethylene bisstearic acid amide. , Hexamethylene bisbechenic acid amide, Hexamethylene hydroxystearic acid amide, Ethylene bisoleic acid amide, Ethylene biserucate amide, Hexamethylene bisoleic acid amide, N, N'-Distearyl adipate amide, N, N'- Examples thereof include distearyl sebacic acid amide, N, N'-diorail adipic acid amide, N, N'-diorail 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 fatty acid.)
Specific examples of the methylol amide include methylol palmitate amide, methylol stearic acid amide, methylol bechenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, and methylol erucic acid amide.

-Ester amide: The ester amide is represented by the following general formula (6).
General formula (6) R11-CONH-R12-OCO-R13
(In the formula, R11 and R13 represent residues obtained by removing COOH from fatty acids, 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 the ester amide include stearoamide ethyl stearate and oleyl amide ethyl urealate.
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, a saturated fatty acid having 12 to 22 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms is preferable, and a saturated fatty acid having 16 to 18 carbon atoms and / or 18 to 22 carbon atoms. Unsaturated fatty acids are more preferred. Lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid are particularly preferable as the saturated fatty acids, and oleic acid and erucic acid are particularly preferable as the unsaturated fatty acids.
Further, nitrified cotton, cellulose acetate propionate resin, and cellulose acetate butyrate resin can be contained in the ink composition for the purpose of improving blocking resistance and the like.

(Nitrocellulose)
As the nitric acid cotton, nitric acid cotton conventionally used in a gravure ink composition or the like can be used. The nitric acid cotton is obtained as a nitrate ester in which three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in the natural cellulose are replaced with a nitric acid group by reacting natural cellulose with nitric acid. As the nitricized cotton used in the present invention, one having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 is preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NC RS-2, (KCNC, KOREA CNC LTD).
(Manufactured by the company) and the like. The amount of nitrocellulose used is preferably in the range of 2.0% by mass or less in the ink composition containing the polyurethane polyurea resin obtained by the present invention.

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

(Cellulose acetate butyrate resin)
As the cellulose acetate butyrate resin, the cellulose acetate butyrate resin conventionally used in gravure ink compositions and the like can be used.
Cellulose acetate butyrate resin is obtained by hydrolysis after triesterification with acetic acid and butyric acid. Generally, resins having 2 to 30% by weight of acetylation, 17 to 53% by weight of butyrylation, and 1 to 5% of hydroxyl groups are commercially available. The amount of the 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 an antistatic agent and a plasticizer can be further added to the ink composition containing the polyurethane polyurea resin obtained by the present invention.

[Method for Producing Laminated Printed Matter Using Ink Composition Using Polyurethane Polyurea Resin Obtained According to the Present Invention]
Next, a method of obtaining a laminated printed matter by using the ink composition using the polyurethane polyurea resin obtained by the present invention as a gravure ink composition for lamination will be described. The polyurethane polyurea resin obtained by the present invention can be used for applications other than laminating and for gravure.
The method for obtaining a laminated printed matter includes at least the following printing method. For example, the gravure ink composition for laminating is printed at least once or more on a known resin film as a base material for laminating by a gravure printing method. Next, another gravure ink composition for laminating is printed by a gravure printing method at an arbitrary position on the surface side (lower layer side when viewed from the surface layer after the final laminating) of the gravure ink composition for laminating formed by these printings. And dry with a dryer.
A laminated printed matter for a packaging bag or the like can be obtained by laminating a resin film or the like by various methods on the side of the layer of the gravure ink composition for laminating the printed matter obtained by the above method. The laminating method includes an extrusion laminating method in which an anchor coating agent is applied to the surface of a printed matter and then a molten polymer is laminated, and a dry method in which an adhesive is applied to the surface of the printed matter and then a film-like polymer is bonded. Lamination method is available.

The above-mentioned extrusion laminating method is known after applying an anchor coating agent such as titanium-based, urethane-based, imine-based, or polybutadiene-based to the surface of a printed matter containing a layer of a gravure ink composition for laminating, if necessary. It is a method of laminating a molten polymer by an extrusion laminating machine, and further, a molten resin can be laminated as an intermediate layer in a sandwich shape with other materials.
As the molten polymer used in the extruded laminating method, conventionally used resins such as low-density polyethylene, ethylene-vinyl acetate copolymer, and polypropylene can be used. Among them, if low-density polyethylene, which is easily oxidized during melting and easily generates a carbonyl group, is used, the effect of the present invention is enhanced.

Further, the above dry laminating method 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 laminating, and then a film-like polymer is bonded by a known dry laminating machine. is there. As the resin for the film used in the dry laminating method, polyethylene, unstretched polypropylene and the like can be used. In particular, in order to obtain a packaging material used for retort pouch applications, an aluminum foil may be sandwiched between a base material and a resin film to be bonded. Such a laminated product can also be used for boiled retort after bag making and filling the contents.
Examples of the resin film used at this time include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, vinylon and the like. Further, as these resin films, it is possible to use a film obtained by processing a resin film such as coating and kneading an antifogging agent, surface coating of a matting agent, and kneading in advance.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass%" and "part" means "parts by mass". In addition, the number of the amount of each material in the table is also "part by mass". The unit of acid value is mgKOH / g.

<Manufacturing method of ketimine solution 1>
51 parts of isophorone diamine, 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.
<Manufacturing method of 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.
<Manufacturing method of ketimine solution 3>
51 parts of isophorone diamine, 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.
<Manufacturing method of 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 (ketimization 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was 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, the mixture was cooled to near room temperature, 25.6 parts of ketimine solution 1 was added, and the mixture was stirred for 30 minutes to obtain PU-1 (solid content: 30% by mass). ..

<Production method of PU-2 (ketimization 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was charged and reacted at 90 to 100 ° C. for 6 hours while introducing nitrogen gas.
Then, after adding 803 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 34 parts of ketimine solution 2 was added, and the mixture was stirred for 30 minutes to obtain PU-2 (solid content: 30% by mass).

<Production method of PU-3 (ketimization 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was 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, the mixture was cooled to near room temperature, 29.2 parts of ketimine solution 3 was added, and the mixture was stirred for 30 minutes to obtain PU-3 (solid content: 30% by mass). ..

<Production method of PU-4 (ketimization 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was charged and reacted at 90 to 100 ° C. for 6 hours while introducing nitrogen gas.
Then, after adding 796 parts of propyl acetate and 199 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 43 parts of ketimine solution 4 was added, and the mixture was stirred for 30 minutes to obtain PU-4 (solid content: 30% by mass).

<Production method of PU-5 (Acetone is charged 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was 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, 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. , 17.4 parts of acetone was added and stirred for 30 minutes to obtain PU-5 (solid content 30% by mass).

<Method for producing PU-6 (diamine is used to add diethyl ketone after chain extension and terminal termination)>
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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was 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, 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 was added and stirred for 30 minutes to obtain PU-6 (solid content 30% by mass).

<Production method of PU-7 (add 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was 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, 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. , 21 parts of methyl ethyl ketone was added and stirred for 30 minutes to obtain PU-7 (solid content 30% by mass).

<Production method of PU-8 (diacetone alcohol is charged 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 adipatediol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and tetrabutyl titanate 0 A .04 portion was 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 size of 4.5 μm

<Production Examples of Ink Compositions of Examples and Comparative Examples>
The pigment, polyurethane resin varnish (PU-1 to PU-8), silica and solvent were kneaded using a paint conditioner manufactured by Red Devil Co., Ltd. to obtain the 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, stored at 60 ° C. for 30 days, and then the stability over time of the ink composition was used as the following evaluation criteria based on the presence or absence of visual precipitation of the pigment. Therefore, it was evaluated. The results are shown in Table 1.
◯: No sedimentation is observed.
Δ: Sedimentation is observed, but it recovers by shaking.
X: Sedimentation is observed, and it does not recover even by shaking.

<Manufacturing 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) to reduce the viscosity. An ink composition having an adjusted density was obtained by adjusting the number to 15 seconds.
Using each of the obtained ink compositions, a printed matter was obtained by printing and drying on the treated surface of a polypropylene film (P-2161 manufactured by Toyobo Co., Ltd.) under the following conditions.
Furthermore, the obtained printed matter was evaluated for the ketimine odor. The specific evaluation method is shown below.

(Printing method / printing conditions)
Room environment at the time of printing: temperature 25 ° C, humidity 50%
Coating machine: Gravure printing machine
Coating speed: 150m / min
Printing plate: Direct 175 lines 28 μm Solid plate Drying temperature: 55 ° C

(Evaluation method for kechimin odor of printed matter)
The printed surface of each of the obtained printed matter was put on the nose, and the odor was evaluated by a sensory test according to the following criteria. The results are shown in Table 1.
◯: No ketimine odor is observed.
Δ: A slight ketimine odor is observed.
X: A 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 were excellent in stability over time as an ink composition. In addition, there was no ketimine odor in the printed matter after it was printed.
On the other hand, the ink compositions of Comparative Examples 1 to 5 using the polyurethane polyurea resin which was not ketiminated were inferior in stability with time as the ink composition. In addition, there was a ketimine odor in the printed matter after it was made into printed matter.

Claims (3)

Urethane prepolymer is synthesized from diol compound and diisocyanate compound,
Next, the urethane prepolymer and a chain extender and / or a reaction terminator in which the amino group of the polyamine compound is ketiminated by a ketone compound under solvent-free conditions are reacted in a polar organic solvent, and the terminal is ketimine. A method for producing a modified polyurethane polyurea resin. The claim that the chain extender and / or the reaction terminator is a chain extender and / or a reaction terminator that is ketiminated by one or more selected from acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol as the ketone compound. The method for producing a polyurethane polyurea resin having a ketiminated terminal according to 1. The method for producing a polyurethane polyurea resin having a ketiminated end according to claim 1 or 2, wherein only the chain extender is ketiminated.