JP6900668B2 - Aqueous composite resin and its manufacturing method - Google Patents

Description

The present invention relates to an aqueous composite resin and a method for producing the same.

In recent years, from the viewpoint of energy saving, low cost, and reduction of environmental load, the development of water-based inks that can exhibit excellent adhesion and coating film resistance to non-polar film substrates has been developed in various ink markets such as gravure, flexo, and inkjet. I'm in a hurry. Acrylic resin having excellent pigment dispersibility and abrasion resistance and urethane resin having excellent substrate adhesion are used for these water-based inks. Further, in order to utilize the advantages of each resin, a blend system of an acrylic resin and a urethane resin and a composite resin are also being actively studied. However, in general, since the compatibility between the acrylic resin and the urethane resin is not good, the coating film resistance cannot be improved by simple blending or compounding, but rather the coating film becomes fragile and the coating film resistance is significantly deteriorated. There was a tendency to do.

Patent Document 1 discloses a core-shell type composite resin for water-based ink in which the shell component is a water-based urethane resin and the core component is an acrylic resin. We are trying to improve the coating resistance by introducing a hydrazide group into a urethane resin and a keto group into an acrylic resin and cross-linking between different resins at room temperature. However, in this design, the compatibility between the urethane resin and the acrylic resin before cross-linking is poor, and even if cross-linking is finally performed, the coating film resistance is not dramatically improved. Moreover, since it is an emulsion type, the pigment dispersibility is extremely poor.

Patent Document 2 discloses an acrylic / urethane composite resin for water-based inks in which an acrylic portion is grafted by introducing an ethylenically unsaturated group into a urethane skeleton and copolymerizing it with an ethylenically unsaturated monomer. .. However, in this method, the urethane resin portion has a three-dimensionally high molecular weight. Therefore, the motility of the molecular chain is reduced, and the compatibility between the urethane portion and the acrylic portion is also significantly reduced. Therefore, the resins cannot be sufficiently fused under low temperature drying conditions, and excellent coating film resistance cannot be exhibited. .. This type is also inferior in pigment dispersibility.

Patent Document 3 discloses an acrylic / urethane composite resin for water-based ink in which a mercapto group is introduced at the end of a urethane resin and an acrylic portion is grafted by a chain transfer reaction. With this method, it is possible to avoid increasing the three-dimensional molecular weight of the urethane portion. However, this resin has problems such as water friction resistance, scratch resistance, and adhesion to a non-polar film substrate.

JP-A-1995-188353 JP-A-1995-082456 Japanese Patent Application Laid-Open No. 2000-345902

A water-based composite resin that has excellent compatibility between dissimilar resins and exhibits excellent water friction resistance, scratch resistance, and adhesion to non-polar film substrates even under low-temperature drying conditions, and water-based ink compositions using the same. For the purpose of provision.

（一般式（１）中、Ｘは−ＯＨ、−ＮＨ_２、−ＮＨＲ_１、−ＳＨからなる群より選ばれる少なくとも一種であり、Ｒ_１はアルキル基である。
Ｒはアルキレン基、アリーレン基、およびアルキレンオキシ基からなる群より選ばれる少なくとも一種の２価の基である。） That is, the present invention
Both-terminal mercapto group-containing urethane formed by reacting a urethane prepolymer (C-1) formed by reacting a polyol (A) with a polyisocyanate (B) with a compound (D) represented by the general formula (1). Ethylene unsaturated monomer containing a carboxyl group-containing ethylenically unsaturated monomer (e-1) and an amino group-containing ethylenically unsaturated monomer (e-2) using a urethane resin (C-2) as a chain transfer agent. The present invention relates to an aqueous composite resin (F) obtained by polymerizing a monomer (E).

General formula (1)

(In the general formula (1), X is at least one selected from the group consisting _{of -OH, -NH 2} , -NHR _{1 , and -SH, and R 1} is an alkyl group.
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkyleneoxy group. )

The present invention relates to the aqueous composite resin in which the compound (D) represented by the general formula (1) is an aminoalkanethiol.

The present invention relates to the aqueous composite resin having an acid value of 15 to 150 mgKOH / g.

The present invention relates to the aqueous composite resin having an amine value of 3 to 35 mgKOH / g.

In the present invention, the amount of the ethylenically unsaturated monomer (E) blended is in the range of 30 to 180 parts by weight with respect to 100 parts by weight of the urethane urea resin (C-2) containing both terminal mercapto groups. Regarding resin.

The present invention relates to an aqueous ink composition containing the aqueous composite resin, a pigment, and a hydrophilic solvent.

The present invention relates to a printed matter having a printed layer formed from the water-based ink composition on a substrate.

（一般式（１）中、Ｘは−ＯＨ、−ＮＨ_２、−ＮＨＲ_１、および−ＳＨからなる群より選ばれる少なくとも一種であり、Ｒ_１はアルキル基である。
Ｒはアルキレン基、アリーレン基、およびアルキレンオキシ基からなる群より選ばれる少なくとも一種の２価の基である。） In the present invention, both ends formed by reacting a urethane prepolymer (C-1) formed by reacting a polyol (A) with a polyisocyanate (B) with a compound (D) represented by the general formula (1). It contains a carboxyl group-containing ethylenically unsaturated monomer (e-1) and an amino group-containing ethylenically unsaturated monomer (e-2) using a mercapto group-containing urethane urea resin (C-2) as a chain transfer agent. The present invention relates to a method for producing an aqueous composite resin (F) obtained by polymerizing an ethylenically unsaturated monomer (E).

General formula (1)

(In the general formula (1), X is at least one selected from the group consisting _{of -OH, -NH 2} , -NHR _{1 , and -SH, and R 1} is an alkyl group.
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkyleneoxy group. )

The aqueous composite resin of the present invention has excellent compatibility between dissimilar resins, and exhibits excellent water friction resistance, scratch resistance, and adhesion to a non-polar film substrate even under low-temperature drying conditions.

First, the acrylic / urethane composite resin which is the aqueous composite resin (F) used in the present invention will be described. The aqueous composite resin (F) of the present invention is a urethane prepolymer (C-1) formed by reacting a polyol (A) with a polyisocyanate (B), and a compound (D) represented by the general formula (1). Can be obtained by synthesizing a urethane urea resin (C-2) containing both terminal mercapto groups by reacting the above, and further polymerizing an ethylenically unsaturated monomer (E) using it as a chain transfer agent.
Specifically, the method for producing the aqueous composite resin (F) of the present invention will be described. First, a polyol (A) and a polyisocyanate (B) are charged into a reaction vessel, and a catalyst is added to cause a reaction to synthesize a urethane prepolymer (C-1) having an isocyanate group at both ends. Subsequently, the compound (D) represented by the general formula (1) is added to the urethane prepolymer (C-1) and reacted. Further, by adding an ethylenically unsaturated monomer (E) and a solvent and adding a radical initiator in a nitrogen atmosphere, a chain transfer reaction occurs, and an acrylic resin is formed from both ends of the urethane urea resin (C-2). The skeleton is grafted.
The ethylenically unsaturated monomer (E) contains a carboxyl group-containing ethylenically unsaturated monomer (e-1) and an amino group-containing ethylenically unsaturated monomer (e-2). ..

<Polyprethane (A)>
Typical examples of the polyol (A) used for the urethane prepolymer (C-1) include a polyether polyol (a-1), a polyester polyol (a-2), a polycarbonate polyol (a-3), and a polyolefin. Examples thereof include based polyols (a-4) and castor oil polyols. Only one kind of these polyols may be used, or a plurality of kinds may be used in combination.

Examples of the polyether polyol (a-1) include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide and tetrahydrofuran, specifically, polyethylene glycol, polypropylene glycol and poly (ethylene / propylene) glycol. , Polytetrahydrofuran glycol and the like. Further, examples thereof include polyether polyols obtained by condensing hexanediol, methylhexanediol, heptanediol, octanediol or a mixture thereof.

Examples of the polyester polyol (a-2) include a polyester polyol in which a polyol component and a dibasic acid component are condensed and reacted. Among the polyols, the diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3'-di. Methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, Cyclohexanediol, bisphenol A and the like can be mentioned, and examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol and the like, and terephthalic acid, adipic acid, azelaic acid and sebatic acid as dibasic acid components. , Diol acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, trimellitic acid and other aliphatic or aromatic dibasic acids, and anhydrides thereof. Examples thereof include polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as ε-caprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone.

Examples of the polycarbonate polyol (a-3) include those obtained by reacting a polyol with a carbonate compound such as a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate. As the polyol constituting the polycarbonate polyol, the polyol exemplified above as a constituent component of the polyester polyol can be used. Further, examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

Examples of the polyolefin-based polyol (a-4) include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene. ..

Castor oil polyol is a biomass polyol made from plant-derived castor oil.

In addition to the above, a low molecular weight diol can be used in combination for the purpose of adjusting the urethane bond concentration and introducing various functional groups. As the low molecular weight diol, a diol having a molecular weight of 500 or less is preferable, and for example,
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, 2-butyl-2- Ethyl-1,3-propanediol, 1,4-butylenediol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-butanetriol, pentaerythritol, sorbitol, N, N-bis ( 2-Hydroxypropyl) aniline, dimethylolacetate, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid and other dimethylolalkanoic acids, dihydroxysuccinic acid and dihydroxypropionic acid. , Dihydroxybenzoic acid and the like.

<Polyisocyanate (B)>
Examples of the polyisocyanate (B) to be reacted with the polyol (A) include aromatic, aliphatic, and alicyclic polyisocyanates. Only one of these may be used, or a plurality of types may be used in combination.

Examples of the aromatic polyisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and lysine diisocyanate. 3,3'-dimethyl-4,4'-biphenylenediocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, 3,3'-dichloro-4,4'-biphenylenediocyanate, 1,5-naphthalene Examples thereof include diisocyanate, 1,5-tetrahydronaphthalenediocyanate.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

A catalyst can also be used in the reaction to obtain the urethane prepolymer (C-1). As the catalyst that can be used, a known metal-based catalyst or amine-based catalyst can be used. Metallic catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), lead 2-ethylhexoate, 2-ethylhexyl titanate, titanium ethylacetate, 2-ethylhexoate. Examples thereof include iron, 2-ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin and the like. Examples of the amine-based catalyst include tertiary amines such as tetramethylbutanediamine. These catalysts are used in the range of 0.001-1 mol% with respect to the polymer polyol.

The reaction for obtaining the urethane prepolymer (C-1) is preferably carried out at 50 to 150 ° C. for 2 to 10 hours. The end point of the reaction can be determined by NCO% measurement by titration.

As the solvent that can be used to obtain the urethane prepolymer (C-1), any solvent can be used as long as it does not react with the isocyanate group. It is preferable to use a solvent that can be easily removed by azeotropic boiling. It is also possible to carry out the reaction without a solvent and later dilute the solvent. Preferred solvents include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Ester solvents such as ethyl acetate, propyl acetate and butyl acetate;
Glycol ester-based solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; and the like can be mentioned.

（一般式（１）中、Ｘは−ＯＨ、−ＮＨ_２、−ＮＨＲ_１、および−ＳＨからなる群より選ばれる少なくとも一種であり、Ｒ_１はアルキル基である。
Ｒはアルキレン基、アリーレン基、およびアルキレンオキシ基からなる群より選ばれる少なくとも一種の２価の基である。） <Compound (D) represented by the general formula (1)>
A urethane urea resin (C-2) having a mercapto group at both ends is obtained by reacting the above-mentioned urethane prepolymer (C-1) with a mercapto group-containing compound (D) represented by the general formula (1).

General formula (1)

(In the general formula (1), X is at least one selected from the group consisting _{of -OH, -NH 2} , -NHR _{1 , and -SH, and R 1} is an alkyl group.
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkyleneoxy group. )

Examples _{of the alkyl group of R 1} include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a dodecyl group. Alkyl groups of numbers 1 to 6 are preferred.
Examples of the alkylene group among R include alkylene groups having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group and a dodecylene group. The number of alkylene groups 1 to 6 is preferable.
Examples of the arylene group include a phenylene group and the like, and examples of the alkyleneoxy group include ethyleneoxy, propyleneoxy and butyleneoxy. R is preferably an alkylene group or a phenylene group.

Examples of the compound (D) represented by the general formula (1) include
Hydroxyalkanethiols such as 2-hydroxyethanethiol, 3-hydroxypropyl-1-thiol, 1-hydroxypropyl-2-thiol, 4-hydroxy-1-butanethiol;
Dithiols such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, etc.
Amino alkanethiols such as 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, 4-amino-1-butanethiol;
Aminobenzene thiols such as 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol;
Can be mentioned.

Among the compounds (D) of the general formula (1), _{aminoalkanethiols in which X is -NH 2} or -NHR ₁ and R is an alkylene group are used in that they are highly reactive and form a urea bond. It is preferable to do so. By introducing the urea bond, the cohesive force of the resin is increased, and the coating film resistance of the resin and the adhesive strength to the base material are improved. Furthermore, by charging so that the number of moles of the isocyanate group is excessive with respect to the number of moles of the amino group, the remaining isocyanate group reacts with the mercapto group to extend the chain, and the urethane prepolymer (C-1) is high. It is molecularized. At this time, since the urea bond is introduced into the urethane resin in addition to both ends, the cohesive force is further improved, and the coating film resistance and the adhesive strength are improved.

When aminoalkanethiol is used as the compound (D) represented by the general formula (1), the amino group preferentially reacts with the isocyanate group in the urethane prepolymer (C-1) to form a urea bond. .. Further, by charging the compound (D) represented by the general formula (1) so that the number of moles of the isocyanate group is excessive with respect to the number of moles, the remaining isocyanate group reacts with the mercapto group to extend the chain. , Urethane prepolymer (C-1) is made high molecular weight. At this time, since the urea bond is introduced into the skeleton of the urethane prepolymer (C-1) in addition to both ends, the cohesive force of the urethane resin is improved and the adhesive strength is improved. Moreover, since the unreacted compound (D) is also reduced, the odor of the resin coating film is also significantly improved.

For the above reasons, when producing the urethane urea resin (C-2) containing both terminal mercapto groups, the isocyanate group of the urethane prepolymer (C-1) is changed to the compound (D) represented by the general formula (1). On the other hand, it is preferable to prepare in excess. Further, the compound (D) represented by the general formula (1) is preferably reacted with respect to 1 mol of the isocyanate group of the urethane prepolymer (C-1) so as to be 0.60 to 0.90 mol. .. When the amount charged is 0.6 mol or more, the acrylic skeleton is easily incorporated into the urethane skeleton, and the desired composite resin is easily obtained. Therefore, the storage stability of the resin solution and the adhesion to the base material are excellent. On the other hand, when the amount is 0.90 mol or less, the amount of the unreacted compound (D) that is not incorporated into the resin is reduced, which is excellent in terms of the odor of the resin coating film.

As the solvent that can be used to obtain the urethane urea resin (C-2) containing both terminal mercapto groups, any solvent can be used as long as it can dissolve the raw material and does not react with the isocyanate group. It is preferable to use a solvent that can be easily removed by azeotropically boiling with water in consideration of the solvent removal step. Preferred solvents include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; glycol ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; Etc., and a ketone solvent is preferable.

<Ethylene unsaturated monomer (E)>
An acrylic / urethane composite resin (F) can be obtained by polymerizing an ethylenically unsaturated monomer (E) using the mercapto group-containing urethane urea resin (C-2) at both ends as a chain transfer agent. At this time, the ethylenically unsaturated monomer (E) contains both the carboxyl group-containing ethylenically unsaturated monomer (e-1) and the amino group-containing ethylenically unsaturated monomer (e-2). It is preferable to polymerize. A carboxyl group, which is an anionic functional group, and an amino group, which is a cationic functional group, coexist in the composite resin to form an acid-base salt, which improves compatibility between the resins, and forms a film and coats the resin. The film strength is increased, and the adhesion to the non-polar film substrate and the water friction resistance are improved.

Examples of the carboxyl group-containing ethylenically unsaturated monomer (e-1) include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, hexahydrophthalic acid β- (meth). ) Acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, carcinic acid and the like, and acrylic acid and methacrylic acid are preferable.

Examples of the amino group-containing ethylenically unsaturated monomer (e-2) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, and diethylaminostyrene. Etc., and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and methylethylaminoethyl (meth) acrylate are preferable.

Further, as the ethylenically unsaturated monomer (E) other than the above, a hydrophilic group-containing ethylenically unsaturated monomer can be used. For example
Sulfonic acid, sodium styrene sulfonate, ammonium styrene sulfonate, lithium styrene sulfonate, 2-acrylamide 2-methyl propane sulfonic acid, sodium 2-acrylamide 2-methyl propane sulfonic acid, metharyl sulfonic acid, sodium metharyl sulfonate , Allyl sulfonic acid, sodium allyl sulfonate, ammonium allyl sulfonate, vinyl sulfonic acid, allyl oxybenzene sulfonic acid, sodium allyl oxybenzene sulfonate, ammonium allyl oxybenzene sulfonate, etc. body;
Basic phosphoric acid content such as 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, etc. Unsaturated monomer;
Polyethylene glycol mono (meth) acrylate (manufactured by Nippon Oil & Fats Co., Ltd., Blemmer PE-90, 200, 350, 350G, AE-90, 200, 400, etc.) Polyethylene glycol / polypropylene glycol mono (meth) acrylate (manufactured by Nippon Oil & Fats Co., Ltd., Blemmer) 50PEP-300, 70PEP-350, etc.), methoxypolyethylene glycol mono (meth) acrylate (manufactured by Nippon Oil & Fats Co., Ltd., Blemmer PME-400, 550, 1000, 4000, etc.) and other polyethyleneoxy group-containing ethylenically unsaturated monomers;
(Meta) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meta) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmetha Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N- Amid group-containing ethylenically unsaturated monomers such as dimethylacrylamide, N, N-diethylacrylamide, and diacetone (meth) acrylamide;
Hydroxy-group-containing ethylenically unsaturated monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and allyl alcohol;
Etc., but are not particularly limited to these. These can be used alone or in combination of two or more.

Examples of other monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, and phenoxyethyl methacrylate. , Phenoxydiethylene glycol acrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenylacrylate, phenylmethacrylate and other aromatic-containing ethylenically unsaturated monomers ;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate , 2-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate Such as linear or branched alkyl group-containing ethylenically unsaturated monomers;
Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylate and isobonyl (meth) acrylate;
Fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
Keto group-containing ethylenically unsaturated monomer such as 2-acetoacetoxyethyl (meth) acrylate;
Allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol di (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Glycerin dimethacrylate, dimethyloltricyclodecanedi (meth) acrylate, trimethylolpropanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaeristoltetra (meth) acrylate, divinylbenzene, divinyl adipate, isophthalic acid An ethylenically unsaturated monomer having two or more ethylenically unsaturated groups such as diallyl, diallyl phthalate, and diallyl maleate;
Epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;
Etc., but are not particularly limited to these. These can be used alone or in combination of two or more.

The glass transition temperature (Tg) of the acrylic resin portion obtained by polymerizing the ethylenically unsaturated monomer (E) described above is preferably in the range of −10 to 60 ° C. When the glass transition temperature is −10 ° C. or higher, the acrylic resin portion is hard and has excellent blocking resistance. On the other hand, when the glass transition temperature is 60 ° C. or lower, the motility of the molecular chain under low temperature drying is not easily impaired, so that the adhesive strength is excellent.

The above glass transition temperature refers to a theoretical value calculated from the following FOX equation.
<FOX type>
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... Wn / Tgn
[In the above FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n kinds of monomers is Tgi (K), and the mass fraction of each monomer is Wi. (W1 + W2 + ... Wi + ... Wn = 1). ]

In the process of compounding acrylic and urethane, the amount of the ethylenically unsaturated monomer (E) is 30 to 180 parts by weight with respect to 100 parts by weight of the urethane urea resin (C-2) containing mercapto groups at both ends. Is preferable. Within the above range, the dispersion stability of the resin is improved. In addition, the hardness of the coating film is improved, and it is excellent in water friction resistance and blocking resistance, and is also excellent in adhesion to a non-polar film substrate.

As the radical initiator used in the acrylic / urethane composite reaction, a known oil-soluble polymerization initiator can be used, and for example, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylhydroperoxide, tert- Organic peroxides such as butylperoxy (2-ethylhexanoate), tert-butylperoxy-3,5,5-trimethylhexanoate, di-tert-butylperoxide;
2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 Azobis compounds such as'-azobis-cyclohexane-1-carbonitrile can be mentioned.

The radical initiator is preferably used in the range of 0.1 to 0.5 parts by weight with respect to 100% by weight of the ethylenically unsaturated monomer (E). If it is less than 0.1% by weight, the polymerization reaction does not proceed sufficiently, the raw material components remain, and there is a risk of deteriorating stability over time, odor and the like. On the other hand, if it exceeds 0.5 parts by weight, the mercapto group-containing urethane urea resin (c-2) at both ends does not chain transfer to the mercapto group, and the acrylic resin component generated independently increases, so that the adhesive strength deteriorates. May be done.

As the solvent used in the reaction, any solvent can be used as long as it dissolves the raw material and the product, but a solvent that can be easily removed by azeotropically boiling with water in consideration of the subsequent solvent removal step. It is preferable to use. Preferred solvents include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; glycol ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate;
Alcohol-based solvents such as ethanol, isopropyl alcohol, n-propanol, isobutanol n-butanol;
And so on. These solvents may be used alone or in combination of two or more.

As a preferable method for making the composite resin of the present invention aqueous, first, ion-exchanged water and a basic compound are added to the reaction-completed composite resin and stirred. The basic compound is used as a neutralizing agent when the hydrophilic group of the composite resin is anionic and unneutralized. When the whole becomes uniform, the solvent removal treatment is started to remove the organic solvent. If necessary, an aspirator or a vacuum pump can be used to remove the solvent, and the solvent can be removed under reduced pressure.

Examples of the basic compound used as the above-mentioned neutralizing agent include, for example.
Ammonia, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2- Examples thereof include amines such as ethyl-1-propanol and pyridine, inorganic alkalis such as sodium hydroxide and potassium hydroxide, and ammonia and trialkylamine are preferable.

The acid value of the composite resin is preferably in the range of 15 to 150 mgKOH / g. Within the above range, the dispersion stability of the composite resin is good, so that the stability over time is excellent, and the adhesion to the base material and the coating film resistance are improved. Furthermore, since the resin coating film has good drying properties, it has excellent blocking resistance and reduces odor.

The amine value of the composite resin is preferably in the range of 3 to 35 mgKOH / g. By coexisting the carboxyl group-containing ethylenically unsaturated monomer (e-1) within the above range, an acid-base salt is formed between the functional groups, so that the compatibility between the resins is improved. The film-forming property and the strength of the resin coating film are increased, and the adhesion to the non-polar film substrate and the water friction resistance are improved.

<Aqueous ink composition>
The water-based ink composition of the present invention is an ink composition containing the water-based composite resin, a pigment, a hydrophilic solvent, and water.

The composite resin of the present invention is preferably used in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight, in terms of solid content in 100% by weight of the aqueous ink composition. If the amount of the composite resin added is less than 5% by weight in terms of solid content, the dispersion stability, storage stability, and coating film physical properties (base material adhesion, water friction resistance) of the ink may deteriorate. On the other hand, when the composite resin exceeds 40% by weight in terms of solid content, the viscosity of the ink composition increases remarkably, drying defects occur in the coating film, and the physical properties of the coating film (base material adhesion, water friction resistance, water resistance blocking). Sex) may decrease.

As the pigment, for example, an achromatic pigment such as carbon black, titanium oxide, or calcium carbonate or a chromatic organic pigment can be used. Organic pigments include insoluble azo pigments such as Truizin Red, Truizin Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red, soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, Arizarin, Indantron, and Thioindigo Derivatives from building dyes such as Maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridon magenta, perylene organic pigments such as perylene red and perylene curlet, isoindolinone yellow , Isoindolinone-based organic pigments such as Isoindrinone Orange, Pyranslon-based organic pigments such as Pyranthron Red, Pyranthron Orange, Thioindigo-based organic pigments, Condensed Azo-based organic pigments, Benzimidazolone-based organic pigments, Kinoftalone yellow, etc. Isoindrin-based organic pigments such as quinophthalone-based organic pigments, isoindrin-ello, and other pigments such as flavanthron ero, acylamide ero, nickel azo ero, copper azomethine ero, perinone orange, anthron orange, dianthraquinonyl red, Examples thereof include dioxazine violet.

To exemplify organic pigments by color index (CI) number, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86 93, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153 154, 155, 166, 168, 180, 185, C.I. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment Green 7, 36, C.I. I. Pigment Brown 23, 25, 26 and the like.

Specific examples of carbon black include "Special Black 350, 250, 100, 550, 5, 4, 4A, 6" manufactured by Degusa, "Printex U, V, 140U, 140V, 95, 90, 85, 80, 75, 55," 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot's" REGAL 400R, 660R, 330R, 250R "" MOGUL E, L ", Mitsubishi Chemical Corporation "MA7, 8, 11, 77, 100, 100R, 100S, 220, 230" "# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 45L, # 44, # 40, # 33, # 332, # 30 , # 25, # 20, # 10, # 5, CF9, # 95, # 260 "and the like.

Specific examples of titanium oxide include "Tapake CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58-" manufactured by Ishihara Sangyo Co., Ltd. 2,85 ”“ Typake R-820,830, 930, 550, 630, 680, 670, 580, 780, 780-2, 850, 855 ”“ Typake A-100, 220 ”“ Typake W-10 ”“ Typake PF-740, 744 "" TTO-55 (A), 55 (B), 55 (C), 55 (D), 55 (S), 55 (N), 51 (A), 51 (C) "" "TTO-S-1, 2" "TTO-M-1, 2", "Titanics JR-301, 403, 405, 600A, 605, 600E, 603, 805, 806, 701, 800, 808" manufactured by TAYCA Corporation. Examples thereof include "Titanics JA-1, C, 3, 4, 5" and "Typure R-900, 902, 960, 706, 931" manufactured by DuPont. Organic pigments such as yellow, magenta, cyan, and black are preferably blended in a proportion of 5 to 30% by weight based on 100% by weight of the aqueous ink composition. Further, in the case of white titanium oxide, it is usually preferable to blend in a proportion of 10 to 60% by weight.

Examples of the hydrophilic solvent include ethanol, 1-propanol (n-propanol), 2-propanol (isopropyl alcohol), 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol. Monovalent alcohol solvent such as;
Ethylene glycol, 1,3-propanediol, propylene glycol, 1,2-butanediol, 1,4-butanediol, pentylene glycol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol , Glycol-based solvents such as tetraethylene glycol;
Ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol dimethyl ether, Glycol ether-based solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether;
Lactam solvents such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam;
Examples thereof include amide solvents such as formamide, N-methylformamide, N, N-dimethylformamide, Idemitsu Equamid M-100 and Equamid B-100, and monohydric alcohol solvents and glycol ether solvents are preferable.
These can be used alone or in combination of two or more.

The aqueous ink composition of the present invention contains, as a pigment dispersion resin, a (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, a styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, Styrene- (meth) acrylic acid copolymer, maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene -Maleic acid half ester copolymer, aqueous urethane resin, etc. can be used. The aqueous composite resin of the present invention is easily compatible with these pigment-dispersed resins and has excellent film-forming properties, so that it exhibits good coating film resistance. A commercially available product may be used as the pigment dispersion resin.

As commercially available products, for example, BASF Corp. JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL62J, JONCRYL63J, JONCRYLHPD-96J, JONCRYL501J, JONCRYLPDX-6102B, manufactured by BYK Chemie DISPERBYK, DISPERBYK180, DISPERBYK187 , DISPERBYK190, DISPERBYK191, DISPERBYK194, DISPERBYK2010, DISPERBYK2015, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2155, SOLSPERS41000 manufactured by AstraZeneca, SMA1000H, SMA1440H, SMA2000H, SMA2000H

Further, the water-based ink composition of the present invention may be used in combination with a resin fine particle dispersion containing a carbodiimide group for the purpose of further improving water friction resistance and water blocking resistance. Since the composite resin of the present invention has a hydrophobic urethane skeleton, the compatibility with the carbodiimide group-containing resin fine particle dispersion at the time of film formation is good, and the carboxyl group and the carbodiimide group of the composite resin react with each other. The water-based friction resistance of the ink coating film is further improved.

As the carbodiimide group-containing resin fine particle dispersion, aqueous dispersion in which a hydrophilic group is modified in polycarbodiimide produced from dicyclohexylmethane-4,4'-diisocyanate or 1,3-bis (2-isocyanato-2-propyl) benzene. The body etc. can be mentioned. Examples of commercially available products include Carbodilite E-02, E-03A, SV-02, V-02, V-02-L2, V-04, E-04 and the like manufactured by Nisshinbo.

The amount of the carbodiimide group-containing resin fine particle dispersion added is preferably about 0.5 to 10% by weight in terms of solid content in 100% by weight of the aqueous ink composition. If the addition amount is less than 0.5% by weight, the effect of improving the water friction resistance and the water blocking resistance may not be confirmed because the addition amount is small. On the other hand, if it exceeds 10% by weight, the dispersion stability and storage stability of the ink may deteriorate.

Further, in the water-based ink composition of the present invention, a commercially available wax fine particle dispersion can be used for the purpose of improving the abrasion resistance of the coating film. Examples of the wax resin fine particle dispersion include Chemipearl W100, W200, W300, W310, W306, W400, W401, W4005, W410, W500, WF640, W700, W800, W900, W950, WH201, WP100, etc. Can be mentioned.

The amount of the wax fine particle dispersion added is about 1 to 5% by weight in terms of solid content in 100% by weight of the aqueous ink composition in consideration of the balance between the improvement of the abrasion resistance in the physical characteristics of the coating film and the adverse effect on the hue. Is preferable.

Further, in the water-based ink composition of the present invention, various surface conditioners can be used for the purpose of adjusting the leveling property on the substrate. Examples of the surface conditioner include Surfinol 104E, 104H, 104A, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, PSA-336, 61, 2502 manufactured by Nissin Chemical Co., Ltd. , Dynol 604, 607, BYK-381, 3441, 302, 307, 325, 331, 333, 342, 345, 346, 347, 348, 349, 378, 3455 and the like, but are not limited thereto.

The amount of the surface conditioner added is preferably about 0 to 1.0% by weight in terms of solid content in 100% by weight of the aqueous ink composition in consideration of the balance of adverse effects on the physical characteristics of the coating film.

Further, in the water-based ink composition of the present invention, a hydrazide-based additive can be used for the purpose of improving the adhesion to the substrate, cross-linking the resin at room temperature (in the case of containing a keto group), and the like. Examples of the hydrazide-based additive include adipic acid hydrazide and the like.

The water-based ink composition of the present invention exhibits good substrate adhesion, water friction resistance and scratch resistance on a non-polar film substrate such as polyethylene terephthalate or polyolefin even under low-temperature drying conditions. Therefore, in recent years, it is very useful in the fields of various inks such as flexo, gravure, and inkjet, which are strongly required to be water-based and expand the base material. Further, it can be used for the purpose of improving the physical characteristics of the coating film even for a penetrating base material such as high-quality paper and a conventional base material such as art paper and coated paper.

Although it is a drying step of the water-based ink composition, it is possible to apply an arbitrary temperature as long as it does not adversely affect the base material. In flexographic printing, gravure printing, and inkjet printing, it is common to process at a low temperature of 40 to 100 ° C. for 1 to 200 seconds.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention at all. In the examples, "parts" represents "parts by weight" and "%" represents "% by weight".

<Manufacture of urethane urea resin containing mercapto groups at both ends>
[Manufacturing Example 1]
Polytetramethylene glycol (PTG-2000, Hodoya Chemical Co., Ltd., number of functional groups 2, hydroxyl value 57.0 mgKOH / g) 51.5 parts, polyester as polyol (A) in a reaction vessel equipped with a stirrer, thermometer, and recirculator. 34.9 parts of a system polyol (P-2010 functional group number 2 hydroxyl value 56.0 mgKOH / g manufactured by Kuraray) and 13.6 parts of isophorone diisocyanate as polyisocyanate (B) were charged and raised to 80 ° C. while stirring in a nitrogen atmosphere. I warmed it up. 0.02 part of titanium diisopropoxybis (ethylacetacetate) was added thereto as a catalyst, the temperature was raised to 110 ° C., the reaction was carried out for 5 hours, and then the temperature was lowered to 80 ° C. At this time, the weight average molecular weight of the produced urethane prepolymer (C-1) was 12700. Subsequently, 40.0 parts of methyl ethyl ketone and 2.3 parts of 2-aminoethanethiol as compound (D) were added, and the mixture was reacted at 75 ° C. for 2 hours. The end point of the reaction was confirmed by FT-IR by disappearance of the peak derived from the isocyanate group ( ^{around 2270 cm -1).} Further, methyl ethyl ketone was added to prepare the final solid content of the resin solution to 70.0%. The acid value of the obtained urethane urea resin (C-2) containing both terminal mercapto groups was 0 mgKOH / g, and the weight average molecular weight was 19,600.

[Acid value]
It is the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin. The dried resin was calculated by potentiometric titration with a potassium hydroxide / ethanol solution according to the method described in JIS K2501. For titration, Hiranuma Sangyo Co., Ltd .: automatic titrator COM-1600 was used.

[Weight average molecular weight]
The weight average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography). The dried resin was dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight average molecular weight was measured by the following equipment and measurement conditions.
Equipment: HLC-8320-GPC system (manufactured by Tosoh Corporation)
Column; TSKgel-SuperMultiporeHZ-M0021488
4.6 mm I.D. x 15 cm x 3 (Molecular weight measurement range 20 to about 2 million)
Elution solvent; Tetrahydrofuran standard substance; Polystyrene (manufactured by Tosoh Corporation)
Flow rate: 0.6 mL / min, sample solution usage: 10 μL, column temperature: 40 ° C.

[Quantification of isocyanate groups]
0.5 g of urethane prepolymer was sampled, 10 mL of a 0.2 mol / L (liter) dibutylamine-toluene solution and 25 mL of toluene were added, and the mixture was stirred for 10 minutes. Then, 40 mL of isopropyl alcohol was added, and unconsumed dibutylamine was titrated with a 0.1 mol / L ethanol solution of hydrochloric acid. For titration, an automatic titrator COM-1600 manufactured by Hiranuma Sangyo Co., Ltd. was used. From the difference between this titration value and the blank experiment, the amount of isocyanate groups remaining in the resin (mmol / g) was calculated.

[Manufacturing Examples 2 to 12]
Urethane prepolymer (C-1) was synthesized with the compounding composition shown in Table 1 by the same method as in Production Example 1, and further reacted with the compound (D) represented by the general formula (1) to mercapto both ends. A group-containing urethane urea resin (C-2) was obtained. After the reaction, the same operation as in Production Example 1 was carried out to prepare the final solid content of the resin solution to 70.0%. The acid value and weight average molecular weight of the obtained urethane urea resin containing mercapto groups at both ends were measured in the same manner.

The abbreviations in Table 1 are shown below.
<Polyol>
Uniol D-2000; NOF polypropylene glycol (2 functional groups, OH group value 56.0, molecular weight 2000)
PEG # 2000; polyethylene glycol manufactured by NOF (2 functional groups, OH group value 56.0, molecular weight 2000)
-PTG-2000SN; Polytetramethylene glycol manufactured by Hodogaya Chemical Co., Ltd. (number of functional groups 2, OH group value 57.0, molecular weight 2000)
-P-2010; MPD / AA polyester polyol manufactured by Kuraray (number of functional groups 2, OH value 56.0, molecular weight 2000)
-P-2011; MPD / AA / TPA polyester polyol manufactured by Kuraray (number of functional groups 2, OH value 55.0, molecular weight 2000)
HS2P-203S; Toyokuni Oil Co., Ltd. 1,3PD / SA polyester polyol (number of functional groups 2, OH value 54.6, molecular weight 2000)
T5652; Asahi Kasei Polycarbonate Polyol (2 functional groups, 56.0 OH value, 2000 molecular weight)
GI-1000; Nippon Soda's hydrogenated polybutadiene-based polyol (number of functional groups 2, OH value 64.0, molecule 1000)
<Manufacturing of acrylic / urethane composite resin (F)>
[Example 1]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a recirculator, 142.9 parts (nonvolatile component: 100.0 parts) of the urethane urea resin solution containing both terminal mercapto groups obtained in Production Example 1 and methyl methacrylate were placed. Add 40.0 parts, n-butyl methacrylate 40.0 parts, methacrylic acid 10.0 parts, dimethylaminoethyl methacrylate 5.0 parts, styrene 5.0 parts, and isopropyl alcohol 37.0 parts, and stir in a nitrogen atmosphere. While doing so, the temperature was raised to 70 ° C. 20.0 parts of methyl ethyl ketone and 0.35 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as an initiator were charged in the dropping funnel and added dropwise to the reaction vessel over 5 hours. The reaction was carried out at 70 ° C. for 8 hours to complete the graft reaction of the acrylic resin portion. After the reaction, 300.0 parts of ion-exchanged water and 7.9 parts of 25% ammonia water were added to neutralize the mixture, and then the solvent was removed at 90 ° C. for 4 hours to obtain an aqueous dispersion of an aqueous acrylic / urethane composite resin. It was. The final solid content was adjusted to 25.0% with ion-exchanged water. The acid value of the obtained composite resin was 32.6 mgKOH / g, the amine value was 17.8 mgKOH / g, and the weight average molecular weight was 41800. The acid value and the weight average molecular weight were measured in the same manner as in the urethane urea resin containing mercapto groups at both ends. Further, the acid value of the acrylic portion was calculated from the acid value of the urethane urea resin containing both terminal mercapto groups, the acid value of the composite resin, and the weight ratio of acrylic / urethane, and the value was 65.2 mgKOH / g.

[Amine value]
The amine value was determined by measuring the potential difference using a 0.1 N aqueous hydrochloric acid solution, and then converted to the equivalent of potassium hydroxide. The amine value indicates the amine value (mgKOH / g) of the resin solid content.

[Examples 2 to 18 and Comparative Examples 1 and 2]
A composite resin was synthesized by the same method as in Example 1 with the compounding composition shown in Table 2. After the reaction, the solvent was removed in the same manner as in Example 1 to obtain an aqueous dispersion of the target aqueous composite resin. The final solid content of the aqueous dispersion of the obtained composite resin was adjusted to 25.0%. The acid value and the like of the obtained resin were measured in the same manner as in Example 1. In Comparative Example 2, neutralization is not necessary.

The abbreviations in Table 2 are shown below.
-PME-400: NOF methoxypolyethylene glycol methacrylate (9 moles of ethylene oxide added)

<Manufacturing of water-based ink composition>

<Manufacturing of white ink composition>
[Example 19] Titanium oxide-based inorganic pigment [Typake CR80 manufactured by Ishihara Sangyo Co., Ltd.] 40.5 parts, John Krill 67 (styrene / acrylic resin) aqueous solution (solid content 25%) 13.5 parts, ion-exchanged water 11.0 Parts, surface conditioner [Surfinol 420 manufactured by Nisshin Kagaku Kogyo Co., Ltd.] 0.2 parts, 0.3 parts of adipic acid hydrazide, 2.0 parts of n-propanol were dispersed in a paint conditioner for 2 hours to disperse concentrated white pigment. I got the liquid. In 67.5 parts of this concentrated white pigment dispersion, 29.0 parts of the aqueous dispersion of the aqueous composite resin obtained in Example 1, 3.0 parts of Chemipearl W500 (solid content 40.0%), and diethylene glycol monoethyl ether After adding 0.5 part, the mixture was kneaded to obtain the desired white water-based ink composition.

[Examples 20 to 36 and Comparative Examples 3 and 4]
The compounding compositions shown in Tables 3 and 4 were prepared in the same manner as in Example 19 to obtain a white water-based ink composition.
<Manufacturing of indigo ink composition>
[Example 37]
Phtalocyanin-based organic pigment [Rionol Blue FG7330 manufactured by Toyo Color Co., Ltd.] 17.2 parts, John Krill 67 (styrene / acrylic resin) aqueous solution (solid content 25.0%) 11.6 parts, ion-exchanged water 18.6 parts, Surface conditioner [Surfinol 420 manufactured by Nisshin Kagaku Kogyo] 0.2 parts, 0.2 parts of adipate hydrazide, 2.7 parts of n-propanol were dispersed in a paint conditioner for 2 hours to obtain a concentrated indigo pigment dispersion. It was. Further, 39.5 parts of the aqueous dispersion of urethane / acrylic resin of Example 1, 4.5 parts of Chemipearl W500 (solid content 40.0%) manufactured by Mitsui Chemicals, Inc., 0.5 parts of diethylene glycol monoethyl ether as a hydrophilic solvent, After adding 5.0 parts of ion-exchanged water, the mixture was kneaded to obtain an indigo water-based ink composition.

[Examples 38 to 54 and Comparative Examples 5 and 6]
The compounding compositions shown in Tables 5 and 6 were prepared in the same manner as in Example 37 to obtain an indigo water-based ink composition.

<Evaluation of water-based ink composition>
The above-mentioned water-based ink composition was coated on a treated PET substrate using Flexiproof 100 (Anilox roller 80 lines / cm). After coating, the substrate was heat-treated in an oven at 80 ° C. for 2 minutes to obtain a printed matter coating film for evaluation. Using this, the substrate adhesion, water friction resistance, and scratch resistance were evaluated. The results are shown in Tables 3-6.

[Adhesion to base material]
A cellophane tape (18 mm width manufactured by Nichiban Co., Ltd.) was attached to the printed matter coating film, a peeling test was conducted in the vertical direction, and the substrate adhesion was evaluated from the ratio of the peeled area of the ink.
The evaluation criteria are as follows. (Practical level is ◎ and ○)
◎; No ink peeling ○; Some ink peeling (less than 10%)
Δ: Ink peels off (10% or more, less than 50%)
×: There is considerable ink peeling (50% or more)

[Water resistance]
The printed matter coating was immersed in water for 1 minute. After the immersion, Kanakin (JIS L 0803) was used as the friction element, and the surface of the coating film dipped in water was reciprocated 800 times with a load of 500 g by a Gakushin tester (manufactured by Tester Sangyo Co., Ltd.). The water friction resistance was evaluated from the ratio of the area where the ink was peeled off. The evaluation criteria are as follows. (Practical level is ◎ and ○)
◎; No ink peeling ○; Some ink peeling (less than 5%)
Δ: Ink peeling (5% or more, less than 30%)
×: There is considerable ink peeling (30% or more)

[Scratch resistance]
For each printed matter coating film, the coated surface was rubbed 20 times with a nail to observe the susceptibility to scratches. The evaluation criteria are as follows. (Practical level is ○)
〇; All the printed matter coating film was not scratched ×; One of the printed matter coating films was scratched.

As shown in Tables 3 and 5, the white water-based ink compositions (Examples 19 to 36) and the indigo water-based ink compositions (Examples 37 to 54) using the water-based composite resins of Examples 1 to 18 are printed matter. It was found that the coating film had excellent substrate adhesion, water friction resistance, and scratch resistance, and was at a practical level.
Among the examples, the compound (D) is aminoalkanethiol, the acid value is 15 to 150 mgKOH / g, the amine value is 3 to 35 mgKOH / g, and the amount of the ethylenically unsaturated monomer (E) blended. However, Examples 19, 20, 22, 23, 26, 28, in which an aqueous composite resin in the range of 30 to 180 parts by weight with respect to 100 parts by weight of the urethane urea resin (C-2) containing both terminal mercapto groups was used. The results of 29, 31, 32, and 34 were excellent in substrate adhesion and water friction resistance. This was the same result for the indigo water-based ink composition.
On the other hand, the white water-based ink compositions (Comparative Examples 3 and 4) and the indigo water-based ink compositions (Comparative Examples 5 and 6) using the water-based resins of Comparative Examples 1 and 2 are water resistant as shown in Tables 4 and 6. The friction and scratch resistance were inferior, and the result did not meet the practical level.
From the above, the superiority of the aqueous composite resin of the present invention was proved.

Claims (8)

Both-terminal mercapto group-containing ureta formed by reacting a urethane prepolymer (C-1) formed by reacting a polyol (A) with a polyisocyanate (B) with a compound (D) represented by the general formula (1). down resins of (C-2) as a chain transfer agent, ethylenically unsaturated containing carboxyl group-containing ethylenically unsaturated monomer (e-1) and the amino group-containing ethylenically unsaturated monomer (e-2) An aqueous composite resin (F) obtained by polymerizing a saturated monomer (E) .
The amino group-containing ethylenically unsaturated monomer (e-2) is derived from dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, and diethylaminostyrene. Aqueous composite resin (F), which is at least one selected from the above group.
General formula (1)

(In the general formula (1), X is at least one selected from the group consisting _{of -OH, -NH 2} , -NHR _{1 , and -SH, and R 1} is an alkyl group.
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkyleneoxy group. ) The aqueous composite resin according to claim 1, wherein the compound (D) represented by the general formula (1) is an aminoalkanethiol. The aqueous composite resin according to claim 1 or 2, wherein the acid value is 15 to 150 mgKOH / g. The aqueous composite resin according to any one of claims 1 to 3, wherein the amine value is 3 to 35 mgKOH / g. The amount of ethylenically unsaturated monomer (E) is one of claims 1 to 4 at both ends the mercapto group-containing urethanes resins (C-2) is in the range of 30 to 180 parts by weight per 100 parts by weight The water-based composite resin described above. An aqueous ink composition containing the aqueous composite resin according to any one of claims 1 to 5, a pigment, and a hydrophilic solvent. A printed matter having a printed layer formed from the water-based ink composition according to claim 6 on a substrate. Both-terminal mercapto group-containing ureta formed by reacting a urethane prepolymer (C-1) formed by reacting a polyol (A) with a polyisocyanate (B) with a compound (D) represented by the general formula (1). down resins of (C-2) as a chain transfer agent, ethylenically unsaturated containing carboxyl group-containing ethylenically unsaturated monomer (e-1) and the amino group-containing ethylenically unsaturated monomer (e-2) A method for producing an aqueous composite resin (F) obtained by polymerizing a saturated monomer (E).
The amino group-containing ethylenically unsaturated monomer (e-2) is derived from dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, and diethylaminostyrene. A method for producing an aqueous composite resin (F), which is at least one selected from the above group .
General formula (1)

(In the general formula (1), X is at least one selected from the group consisting _{of -OH, -NH 2} , -NHR _{1 , and -SH, and R 1} is an alkyl group.
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkyleneoxy group. )