JP2018184581A - Resin composition aqueous dispersion for inkjet ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin aqueous dispersion for inkjet ink that shows excellent adhesion to a nonpolar group material such as polyolefin resin including polypropylene without impairing the mechanical strength of a polyolefin resin composition, and also has excellent water dispersion.SOLUTION: The present invention provides a resin composition aqueous dispersion for inkjet ink (Q) containing polyurethane resin (A), acid-modified polyolefin (X) and aqueous medium; and an inkjet ink (J) containing the resin composition aqueous dispersion for inkjet ink (Q), a pigment (P) and a moisture retention stabilizing aid (M).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition aqueous dispersion for inkjet ink.

  2. Description of the Related Art Inkjet recording methods are widely used because various types of high-quality images can be recorded on various types of recording media by ejecting ink from a large number of nozzles provided in an inkjet head in the form of droplets. In particular, printing on outdoor signboards using the inkjet method has been intensively studied by improving the technology of pigment dispersions with excellent weather resistance, but polyolefin substrates such as propylene resins are nonpolar because the printing substrate is nonpolar. There is a problem that the fixing property of the pigment cannot be secured. Patent Document 1 describes an ether-based resin having a low solubility parameter that is excellent in adhesion to a polyolefin-based substrate, but it is difficult to sufficiently fix the pigment.

  Patent Documents 2 to 4 describe that various surfactants are used as essential components in order to stably disperse the modified polyolefin resin in an aqueous medium. However, the surfactant is non-volatile and remains in the coating film of the modified polyolefin resin even after drying. The remaining surfactant, when used in a large amount, significantly reduces the water resistance of the coating, and even a small amount can dramatically change the interface properties to improve performance such as adhesion to the substrate. Adversely affect. Furthermore, since the surfactant may bleed out from the coating film, it is not preferable in terms of environment and hygiene, and the performance such as adhesion to the substrate may change over time. is there.

JP2015-120818A JP-A-8-3376 JP-A-8-92427 Japanese Patent No. 2895574

  The problem to be solved by the present invention is to provide an aqueous composite resin dispersion that exhibits excellent adhesion and scratch resistance to non-polar substrates such as polyolefin resins and is excellent in water dispersibility.

As a result of intensive studies, the present inventors have found a resin composition aqueous dispersion for inkjet ink that can solve the above-described problems.
That is, the present invention provides a resin composition aqueous dispersion (Q) for an inkjet ink containing a polyurethane resin (A), an acid-modified polyolefin (X) and an aqueous medium; and the aqueous resin composition for an inkjet ink (Q). ), A pigment (P), and a moisturizing stabilization aid (M).

  By this invention, the resin composition aqueous dispersion which shows the outstanding adhesiveness and abrasion resistance to nonpolar base materials, such as polyolefin resin, and is excellent also in water dispersibility can be obtained.

The resin composition aqueous dispersion (Q) for inkjet ink of the present invention contains a polyurethane resin (A), an acid-modified polyolefin (X), and an aqueous medium.
The polyurethane resin (A) is preferably dispersed in an aqueous medium, and the acid-modified polyolefin (X) is preferably dispersed in an aqueous medium.

  The aqueous medium contained in the aqueous dispersion (Q) is preferably water, but a mixed solvent of water and a hydrophilic solvent can also be used. Examples of hydrophilic solvents include solvents that are substantially non-reactive with NCO groups (such as ketones such as acetone and ethyl methyl ketone, esters, ethers, and amides), and the weight of water and the hydrophilic solvent. The ratio is preferably 100/0 to 50/50, more preferably 100/0 to 80/20, in particular 100/0.

[Polyurethane resin (A)] [Polyurethane resin aqueous dispersion (A1)]
The polyurethane resin (A) is not particularly limited, but preferably has an acid group and / or an acid anion group from the viewpoint of dispersion stability. The polyisocyanate (a), the polyol (b), and a carboxylic acid (salt in the molecule) A polyurethane resin having a compound (d) having a group (α) or a sulfonic acid (salt) group (β) and further containing two or more active hydrogen atom-containing groups in the molecule as an essential constituent raw material is more preferable. .

  Even if the polyurethane resin does not contain (d) as an essential constituent raw material, the polyurethane resin (A) is dispersed in an aqueous medium by using an emulsifier described later to obtain an aqueous dispersion (A1) of the polyurethane resin. Can be manufactured.

  As the polyisocyanate (a), an aromatic polyisocyanate having 2 to 3 or more isocyanate groups (excluding carbon in the NCO group, the same applies hereinafter, hereinafter abbreviated as C) 6 to 20 aromatic polyisocyanate ( a1), C2-18 aliphatic polyisocyanate (a2), C4-15 alicyclic polyisocyanate (a3), C8-15 araliphatic polyisocyanate (a4), and modified products of these polyisocyanates (a5) ) And combinations of two or more thereof.

  As the aromatic polyisocyanate (a1), for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 4,4′- or 2, 4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; trifunctional or more of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)] A mixture of a polyamine and a polyamine]: polyaryl polyisocyanate (PAPI)], 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3 ′ -Dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthy Down diisocyanate, 4,4 ', 4 "- triphenylmethane triisocyanate, m- or p- isocyanatophenyl sulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate (a2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Etc.

  Examples of the alicyclic polyisocyanate (a3) include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanate). Natoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and the like.

  Examples of the araliphatic polyisocyanate (a4) include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

  As the modified polyisocyanate (a5), the modified polyisocyanate (modified urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and / or oxazolidone group) A free isocyanate group content of preferably 8 to 33%, more preferably 10 to 30%, particularly 12 to 29%), for example, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.) And modified polyisocyanates such as urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, and urethane-modified polyisocyanates [excess polyisocyanate (TDI, MDI, etc.) As the polyol used a polyol in the production of free isocyanate-containing prepolymer] obtained by reacting, include low molecular weight polyols described below. Examples of the combination of two or more types include a combination of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer).

  Of these, (a2) and (a3) are preferable, (a3) is more preferable, and IPDI and hydrogenated MDI are particularly preferable.

  The polyol (b) includes a high-molecular polyol (b1) having a hydroxyl equivalent of 150 or more (Mn per hydroxyl group), a low-molecular polyol (b2), and a combination of two or more of these. [In the above and the following, Mn represents a number average molecular weight measured using gel permeation chromatography (GPC). ]

(B1) includes polyester polyol (b11), polyether polyol (b12), polyolefin polyol (b13), and polymer polyol (b14).
(B11) includes condensation type polyester (b111), polylactone polyol (b112), polycarbonate polyol (b113), and castor oil-based polyol (b114).
(B12) includes an alkylene oxide (hereinafter abbreviated as AO) adduct (b121) of an active hydrogen atom-containing compound and a coupling product (b122) thereof.
Of these polyols (b), polyester polyol (b11) and polyether polyol (b12) are preferred.
Of the polyester polyol (b11), polylactone polyol (b112) and polycarbonate polyol (b113) are preferable from the viewpoint of hydrolysis resistance, and polycarbonate polyol (b113) is more preferable.

(B2) includes a divalent to octavalent or higher polyhydric alcohol (b21) and an AO low molar adduct (b22) of an active hydrogen atom-containing compound having a hydroxyl equivalent of 30 or more and less than 150. .
The polyhydric alcohol (b21) includes a dihydric alcohol (b211) and an alcohol (b212) having a 3 to 8 valent hydroxyl group.
Examples of the dihydric alcohol (b211) include C2-18 aliphatic dihydric alcohol (b2111), C4-12 alicyclic dihydric alcohol (b2112), and C6-18 aromatic dihydric alcohol (b2113). included.

Examples of the aliphatic dihydric alcohol (b2111) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, neopentyl glycol, 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol and the like.
Examples of the alicyclic dihydric alcohol (b2112) include low molecular diols having a cyclic group, for example, those described in JP-B No. 45-1474.
Examples of the aromatic dihydric alcohol (b2113) include bis (hydroxymethyl) cyclohexane and bis (hydroxyethyl) benzene.

  Examples of the alcohol (b212) having a 3- to 8-valent hydroxyl group include trimethylolpropane, glycerin, hexanetriol, pentaerythritol, sorbitol, xylitol, and mannitol. These intermolecular or intramolecular dehydrates (diglycerin, dipentaerythritol, sorbitan, etc.), saccharides (glucose, fructose, sucrose, etc.) and derivatives thereof (glycosides, such as α-methylglucoside, etc.); Contains polyols.

  AO used for the production of the AO adduct (b121) and the AO low molar adduct (b22) of the active hydrogen atom-containing compound may be C2-12 or more AO, such as ethylene oxide (EO), 1,2-propylene. Oxide (PO), 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran (THF), α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin) and combinations of two or more thereof (random) And / or block).

  The active hydrogen atom-containing compound (k) used for the production of the polyether polyol (b12) and the AO low molar adduct (b22) of the active hydrogen atom-containing compound is a compound having 2 to 8 or more active hydrogen atoms. Is included. Examples of the compound having an active hydrogen atom include a compound (k1) having a hydroxyl group, a compound (k2) having an amino group, a compound (k3) having a mercapto group, and a compound (k4) having a carboxyl group.

Examples of the compound (k1) having a hydroxyl group include polyhydric alcohol (b212) and polyhydric phenol (k12).
Examples of the polyhydric phenol (k12) include monocyclic polyhydric phenol (k121) and bisphenols (k122).
Examples of the monocyclic polyhydric phenol (k121) include pyrogallol, catechol and hydroquinone.
Examples of the bisphenols (k122) include bisphenol A, bisphenol F, and bisphenol S.

Examples of the compound (k2) containing an amino group include a monoamine (k21) and a polyamine (k22).
Examples of the monoamine (k21) include ammonia (k211), primary monoamine (k212), alkanolamine (k213), and secondary monoamine (k214).
As the primary monoamine (k212), C1-20 monohydrocarbylamine can be used, and examples thereof include butylamine, cyclohexylamine, aniline and benzylamine.
As the alkanolamine (k213), an amine having a C2-4 hydroxyalkyl group can be used, and examples thereof include monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine.

  Examples of the secondary monoamine (k214) include dibutylamine, diethylamine, dimethylamine, and dipropylamine.

Examples of the polyamine (k22) include an aliphatic polyamine (k221), a polyalkylene polyamine (k222), an alicyclic polyamine (k223), an araliphatic polyamine (k224), an aromatic polyamine (k225), and a heterocyclic polyamine (k226). ) Is included.
Examples of the aliphatic polyamine (k221) include ethylenediamine, trimethylenediamine, and hexamethylenediamine.
Examples of the polyalkylene polyamine (k222) include diethylenetriamine.
Examples of the alicyclic polyamine (k223) include dicyclohexylmethanediamine and isophoronediamine.
Examples of the araliphatic polyamine (k224) include xylylenediamine.
Examples of the aromatic polyamine (k225) include phenylenediamine, tolylenediamine, diethyltolylenediamine, diphenylmethanediamine, diphenyletherdiamine, and polyphenylmethanepolyamine.
Examples of the heterocyclic polyamine (k226) include piperazine, N-aminoethylpiperazine, and other compounds described in JP-B No. 55-21044.

  As the compound (k3) containing a mercapto group, a polythiol corresponding to the polyhydric alcohol (b212) (at least a part of OH is substituted with SH), a polythiol obtained by reacting a glycidyl group-containing compound with hydrogen sulfide Etc.

As the compound (k4) containing a carboxyl group, aliphatic dicarboxylic acid (k41), alicyclic dicarboxylic acid (k42), aromatic dicarboxylic acid (k43) and trivalent or higher polycarboxylic acid (k44) are used. it can.
Examples of the aliphatic dicarboxylic acid (k41) include succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid and maleic acid.
Examples of the alicyclic dicarboxylic acid (k42) include dimer acid.
Examples of the aromatic dicarboxylic acid (k43) include terephthalic acid, isophthalic acid, and phthalic acid.
Examples of the trivalent or higher polycarboxylic acid (k44) include trimellitic acid and pyromellitic acid.

  The addition of AO to the active hydrogen atom-containing compound can be carried out at normal pressure or under pressure without any catalyst or in the presence of a catalyst (for example, an alkali catalyst, an amine-based catalyst, an acidic catalyst, etc.) (particularly at the latter stage of the AO addition). It can be performed in one stage or in multiple stages. For example, a method in which an active hydrogen atom-containing compound and a catalyst are charged into a pressure reactor and AO is injected into the pressure reactor may be used. Examples of the catalyst include alkali catalysts such as hydroxides of alkali metals (lithium, sodium, potassium, cesium, etc.); acid catalysts [perhalogen acids (perchloric acid, perbromic acid, periodic acid), sulfuric acid, phosphoric acid and nitric acid] Etc., preferably perchloric acid] and salts thereof [preferably salts of divalent or trivalent metals (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, etc.)] and the like. The reaction temperature is preferably 50 to 150 ° C., and the reaction time is preferably 2 to 20 hours.

When two or more types of AO are used in combination, both block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixture of both [chips after random addition: ethylene oxide chains arbitrarily distributed in the molecule 0 to 50% by weight (preferably 5 to 40% by weight), and 0 to 30% by weight (preferably 5 to 25% by weight) of EO chain may be chipped at the molecular terminals. Among the AOs, preferred are EO alone, PO alone, THF alone, combined use of PO and EO, and combined use of PO and / or EO and THF (in the case of combined use, random, block and mixed system of both).

The number of moles of AO added is preferably 1 to 140, more preferably 1 to 110, and particularly preferably 1 to 90 per active hydrogen atom. When the added mole number is 140 or less, the strength of the obtained polyurethane resin does not decrease.
After completion of the AO addition reaction, if necessary, the catalyst can be neutralized and treated with an adsorbent to remove and purify the catalyst.

Examples of (b121) include polyoxyethylene polyol [polyethylene glycol (hereinafter abbreviated as PEG)], polyoxypropylene polyol [polypropylene glycol (hereinafter abbreviated as PPG), etc.], polyoxyethylene / propylene polyol, polytetramethylene ether, and the like. Examples include EO and / or PO adducts of glycols and bisphenols.
(B122) includes those obtained by coupling two or more molecules of (b121) with an alkylene halide having a C1-6 alkyl group (for example, methylene dichloride).
(B12) desirably has a low degree of unsaturation (preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, particularly preferably 0.02 meq / g or less), and preferably at least 30. %, More preferably at least 50%, particularly preferably at least 70%.

  (B111) is a polycondensation product of a polyol and a compound (k4) containing a carboxyl group, (b112) is a polyaddition product of a lactone (h1) to the polyol, and (b113) is an alkylene carbonate (h2) to the polyol. )), And (b114) includes castor oil and castor oil modified with polyol or AO.

  As the polyol constituting them, the above (b2) and / or (b12) [preferably those having a hydroxyl equivalent weight of 500 or less] can be used.

  As the compound (k4) containing a carboxyl group, dicarboxylic acid can be preferably used. A dicarboxylic acid and a small proportion (20% or less) of a tricarboxylic or higher polycarboxylic acid may be used in combination.

As the lactone (h1), a C4-12 lactone can be used, and examples thereof include 4-butanolide, 5-pentanolide, and 6-hexanolide.
As the alkylene carbonate (h2), C2-8 alkylene carbonate can be used, and examples thereof include ethylene carbonate and propylene carbonate. Two or more of these may be used in combination.

  (B111) is, for example, (k4) or an ester-forming derivative thereof [an acid anhydride (maleic anhydride, phthalic anhydride, etc.), an ester having a C1-4 lower alkyl group (dimethyl adipate, dimethyl terephthalate, etc.) , Acid halides (acid chlorides, etc.)] and an excess equivalent amount of polyol by dehydration condensation polymerization or transesterification reaction, followed by dehydration condensation polymerization or transesterification reaction of (k4) or its ester-forming derivative and polyol with AO. Or by reaction of a polyol with an acid anhydride and AO.

  Examples of (b111) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, polydiethylene adipate diol, Poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polyneopentyl terephthalate diol, etc. Can be mentioned.

  (B112) and (b113) can be produced by polyaddition of (h1) or (h2) using a polyol as an initiator.

  Modified castor oil can be produced by transesterification of castor oil and polyol and / or AO addition.

  Examples of (b112) include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

Examples of (b113) include polyhexamethylene carbonate diol.
As a commercially available product of (b113), Nipponran 980R [Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.], T5652 [Mn = 2,000, manufactured by Asahi Kasei Co., Ltd.] and T4672 [Mn = 2,000, Asahi Kasei Co., Ltd.].
Examples of (b114) include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adduct of castor oil.

Examples of (b13) include polyalkadiene polyol (b131) and acrylic polyol (b132).
Examples of the polyalkadiene-based polyol (b131) include polybutadiene diol [polybutadiene having a 1,2-vinyl structure and / or 1,4-trans structure (butadiene homopolymer and copolymer such as styrene butadiene copolymer, acrylonitrile butadiene copolymer) diol]. And hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%) and the like. Examples of polybutadiene diol include NISSO-PBG series (G-1000, G-2000, G-3000, etc.) (manufactured by Nippon Soda) and Poly Bd (R-45M, R-45HT, CS-15, CN-15, etc.) (Manufactured by ARCO, USA).

  Examples of the acrylic polyol (b132) include hydroxyalkyl (C2-6) (meth) acrylate [ethyl hydroxyethyl (meth) acrylate etc.] and other monomers [styrene and alkyl (C1-8) (meth) acrylate. Etc.].

(B14) includes a polymer-containing polyol obtained by polymerizing a radically polymerizable monomer in situ in a polyol [(b11) and / or (b12) and (b2) if necessary). The monomer includes styrene, (meth) acrylonitrile, (meth) acrylic acid ester, vinyl chloride, and a mixture of two or more thereof. The polymerization of the monomer is preferably performed in the presence of a polymerization initiator.
(B14) is preferably 30 to 70% (more preferably 40 to 60%, particularly preferably 50 to 55%) of a polymerized monomer, that is, a translucent or opaque white or tan color in which a polymer is dispersed in a polyol. Is a dispersion of The hydroxyl value of (b14) is preferably 10 to 300, more preferably 20 to 250, and particularly preferably 30 to 200.

  The hydroxyl equivalent of (b1) is preferably 150 to 5,000, more preferably 250 to 3,000, and particularly preferably 300 to 2,500.

  Among (b), a combination of (b1) and (b1) and a small proportion (for example, 20% or less) of (b2) is preferable, and among (b1), (b12) and (b11) are particularly preferable. Preferred is (b113), and most preferred is a polycarbonate diol having a Mn of 1,000 to 4,000.

  As the compound (d) having a carboxylic acid (salt) group (α) or a sulfonic acid (salt) group (β) in the molecule and further containing two or more active hydrogen atom-containing groups in the molecule, A compound (d1) containing a carboxyl group or its base (α) and two or more active hydrogen atom-containing groups other than the carboxyl group and the sulfonic acid group, and a sulfonic acid (salt) group or its base (β); The compound (d2) containing 2 or more active hydrogen atom containing groups other than a carboxyl group and a sulfonic acid group is mentioned.

Here, the carboxylic acid (salt) group (α) refers to a carboxyl group or a base neutralized with an alkali metal, alkaline earth metal, amine or the like, and the sulfonic acid (salt) group (β) refers to a sulfonic acid. A base or a base neutralized with an alkali metal, alkaline earth metal, amine or the like.

As (d1), carbon number (hereinafter abbreviated as C) 6-24 dialkyrol alkanoic acid can be used. For example, 2,2-dimethylolpropionic acid (abbreviated as DMPA), 2,2-dimethylolbutanoic acid, Examples include 2,2-dimethylol heptanoic acid and 2,2-dimethylol octanoic acid. These salts such as salts of amines (triethylamine, alkanolamine, morpholine, etc.) and / or alkali metal salts (sodium salt, etc.) can also be used.

As (d2), carbon number (hereinafter abbreviated as C) 6-24 dialkylsulfonic acid (d21), C6-24 diaminesulfonic acid (d22), and the like can be used.
(D21) includes 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, 2,2-dimethylolsulfonic acid, 2,2-dimethylolbutanesulfonic acid, 2,2-dimethylolheptane Sulfonic acid, 2,2-dimethyloloctanesulfonic acid, 5sulfo- (dihydroxyethyl) isophthalate, N, Nbis (2-hydroxyethyl) 2-aminoethanesulfonic acid and the like can be used.
As (d22), N- (β-sulfoethyl) ethylenediamine or the like can be used.

As the terminator (e1) that can be used if necessary, a primary monoamine (k212), a secondary monoamine (k214), and a monohydric alcohol (e11) can be used.
The monohydric alcohol (e11) includes an aliphatic alcohol (e111), an aromatic alcohol (e112), and an alicyclic alcohol (e113).
As the aliphatic alcohol (e111), an alcohol having a C1-15 alkyl group can be used, and examples thereof include methanol, ethanol, butanol, decanol, and isopropyl alcohol.
As the aromatic alcohol (e112), an alcohol having a C7-20 aryl group can be used, and examples thereof include benzyl alcohol.
As the alicyclic alcohol (e113), alcohol having a C7-20 alicyclic ring can be used, and examples thereof include cyclohexyl alcohol and cyclopentane alcohol.

  The polyurethane resin (A) has acid groups and / or neutralized acid anion groups, and the total content of acid groups and neutralized acid anion groups based on the weight of the polyurethane resin (A) is the above resin From the viewpoint of the dispersion stability of the composition aqueous dispersion and the ejection stability of the ink, it is preferably 0.2 to 1.0 mmol / g, more preferably 0.4 to 0.8 mmol / g. The dispersion stability is good at 0.2 mmol / g or more, and the ink ejection stability is good at 1.0 mmol / g or less.

The total content of acid groups and / or neutralized acid anion groups of the polyurethane resin can be determined by measuring the acid value of the resin before neutralization.
Total content of acid groups and / or neutralized acid anion groups (mmol / g) = (acid value) /56.1

<Method for measuring acid value>
A predetermined amount of polyurethane resin is dissolved in 50 ml of dimethylformamide (hereinafter referred to as DMF) in a 100 ml flask, and titrated with a 0.1 mol / l potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator ( The end point is the point where the color of the indicator has changed from transparent to light red).

Acid value = 5.61 × a × f / S
a: The number of ml of titration of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution.
f: Potency of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution.
S: Amount of polyurethane resin collected (g)
When the above measurement method is difficult, it can be obtained from the content of the compound (d) containing a hydrophilic group and an active hydrogen atom by the following calculation formula.
Acid group and / or neutralized acid anion group (mmol / g) = [(d) content (g)] × [number of acid groups in one molecule of (d)] × 1000 / {[( d) molecular weight] × x [weight of polyurethane resin (g)]}

In the present invention, the polyurethane resin (A) and the aqueous polyurethane resin dispersion (A1) are preferably synthesized as follows.
First, polyisocyanate (a), polyol (b) and carboxylic acid (salt) (α) group or sulfonic acid (salt) group (β) in the molecule, and two or more active hydrogen atoms in the molecule The urethane prepolymer (A0) is obtained by reacting the compound (d) containing a containing group.

Next, (A0) is neutralized with a neutralizing agent (n) and then dispersed in an aqueous medium. Next, if necessary, it is further mixed with an aqueous medium [optionally containing a chain extender (f) other than water, a cross-linking agent (x) and / or a terminator (e)], and reacted until the isocyanate group is substantially eliminated. Conversion to polyurethane resin aqueous dispersion (A1) containing polyurethane resin (A) by performing [chain extension with water or (f) and optionally crosslinking with (x) and / or termination of reaction with (e)] can do.

  In the case of producing (A), the compound (d) is used as a part of the polyol (b), and the neutralizing agent (n) of the carboxyl group or sulfonic acid group is further produced in the production of (A0). Use before or after production to neutralize.

(A) is manufactured via (A0). Formation of (A0) is preferably carried out by a reaction at 20 ° C. to 150 ° C., more preferably 60 ° C. to 110 ° C., and the reaction time is preferably 2 to 10 hours. (A0) can be formed in the presence or absence of an organic solvent that is substantially non-reactive with the NCO group. The prepolymer preferably has a free NCO group content of 0.5 to 10%.
Examples of the organic solvent substantially non-reactive with the NCO group that can be used as necessary include ketones such as acetone and ethyl methyl ketone, esters, ethers, and amides. Of these, acetone is preferred.

  In the production of the prepolymer, a catalyst may be used in order to accelerate the reaction. Examples of the catalyst include amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine, and cycloamidines described in US Pat. No. 4,524,104 [1,8-diaza-bicyclo (5,4,0) undecene-7 ( San-Apro / Production, DBU), etc.]; tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin octylate; titanium-based catalysts such as tetrabutyl titanate.

  When the compound (d) is used in the production of (A0), the neutralization agent (n) of the carboxyl group or sulfonic acid group may be used for neutralization before or after the production of (A0). it can. Examples of (n) include amines (such as triethylamine, alkanolamine, and morpholine) and alkali metal hydroxides (such as sodium hydroxide and potassium hydroxide).

  The aqueous dispersion (A1) of the polyurethane resin (A) can be obtained by dispersing (A) in an aqueous medium in the absence or presence of an emulsifier.

In the case of a polyurethane resin having (d) as an essential constituent material, an aqueous polyurethane resin dispersion (A1) in which the polyurethane resin (A) is dispersed in an aqueous medium can be produced without using an emulsifier. It is possible to produce an aqueous dispersion (A1) having further excellent dispersibility by using an emulsifier.


On the other hand, in the case of a polyurethane resin that does not use (d) as an essential constituent material, an aqueous dispersion (A1) of a polyurethane resin in which the polyurethane resin (A) is dispersed in an aqueous medium is obtained by using an emulsifier (m). Can be manufactured.

  The emulsifier may be added to either the prepolymer or the aqueous medium or to both. If the emulsifier is reactive with the prepolymer, it is preferably added to the aqueous medium. The addition amount of the emulsifier is preferably 0.2 to 10%, more preferably 0.3 to 6% based on the weight of the urethane prepolymer, but depending on the amount when (d) is used. The amount may be less than the above range.

  The emulsifier (m) includes nonionic (m1), anionic (m2), cationic (m3) and amphoteric surfactants (m4), a polymeric emulsifying dispersant (m5) and two or more of these. Combinations are included, for example, those described in US Pat. No. 3,929,678 and US Pat. No. 4,331,447.

  As (m1), aliphatic alcohol (carbon number 8-24) AO (carbon number 2-8) adduct (polymerization degree = 1-100), (poly) oxyalkylene (carbon number 2-8, polymerization degree) = 1 to 100) higher fatty acid (carbon number 8 to 24) ester [polyethylene glycol monostearate (polymerization degree = 20), polyethylene glycol distearate (polymerization degree = 30), etc.], polyvalent (divalent to 10-valent or More) alcohol fatty acid (carbon number 8-24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan monolaurate, etc.], (poly) oxyalkylene (carbon number 2-8, degree of polymerization = 1-100) Polyvalent (divalent to 10-valent or higher) alcohol higher fatty acid (8 to 24 carbon atoms) ester [polyoxyethylene monolaurate (heavy Degree = 10) Sorbitan and polyoxyethylene (degree of polymerization = 50) dioleic acid methyl glucoside etc.], fatty acid alkanolamide [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, etc.], (poly) Oxyalkylene (2 to 8 carbon atoms, polymerization degree = 1 to 100) alkyl (1 to 22 carbon atoms) phenyl ether, (poly) oxyalkylene (2 to 8 carbon atoms, polymerization degree = 1 to 100) alkyl (carbon number) Examples thereof include 8-24) amino ether and alkyl (C8-24) dialkyl (C1-6) amine oxide [lauryl dimethylamine oxide and the like].

  As (m2), a hydrocarbon ether carboxylic acid having 8 to 24 carbon atoms or a salt thereof, [(poly) oxyethylene (degree of polymerization = 1 to 100) sodium lauryl ether acetate and (poly) oxyethylene (degree of polymerization = 1-100) Disodium lauryl sulfosuccinate, etc.], C8-24 hydrocarbon sulfate salt [sodium lauryl sulfate, (poly) oxyethylene (degree of polymerization = 1-100) sodium lauryl sulfate, (poly) oxy Ethylene (polymerization degree = 1-100) lauryl sulfate triethanolamine and (poly) oxyethylene (polymerization degree = 1-100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.], C8-24 hydrocarbon sulfonic acid Salts [sodium dodecylbenzenesulfonate, etc.] and hydrocarbon phosphates having 8 to 24 carbon atoms Tell salt [sodium lauryl phosphate and (poly) oxyethylene (degree of polymerization = 1-100) sodium lauryl ether phosphate, etc.], fatty acid salt [sodium laurate, triethanolamine laurate, etc.], acylated amino acid salt [palm Oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium and lauroylmethyl -Β-alanine sodium and the like].

  As (m3), alkyl (carbon number 1 to 4) sulfate higher fatty acid aminoalkyl (carbon number 2 to 4) trialkyl (carbon number 1 to 4) ammonium salt [(ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium etc.) ], An amine salt type [diethylaminoethylamide stearate lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.] and the like.

  (M4) is a betaine-type amphoteric surfactant [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxysulfo Betaine and lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl phosphate sodium, etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate etc.].

  As (m5), polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; carboxyl group-containing (co) polymers such as polyacrylic acid soda, and Mn = 1,000 to 50,000 And a polymer type dispersant having a urethane bond or an ester bond described in US Pat. No. 5,906,704 and the like [for example, a polycaprolactone polyol and a polyether diol linked with an organic polyisocyanate (a)] Can be used.

The hydrophilic solvent to be included in the aqueous medium as necessary includes those substantially non-reactive with NCO groups and hydrophilic (water-miscible) solvents (acetones, ketones such as ethyl methyl ketone, esters, ethers). And amides). Of these, acetone is preferred.
The weight ratio of water to hydrophilic solvent is preferably 100/0 to 50/50, more preferably 100/0 to 80/20, and particularly preferably 100/0.
When a hydrophilic solvent is used, these may be distilled off as necessary after forming the aqueous polyurethane resin dispersion.

The apparatus for emulsifying and dispersing in the production of (A1) is not particularly limited, and examples thereof include an emulsifier of the following method.
1) Vertical stirring system 2) Rotor-stator system [eg “Ebara Milder” (manufactured by Ebara Seisakusho)] 3) Line mill system [eg line flow mixer] 4) Static tube mixing type [eg static Mixer], 5) Vibration type [e.g. "VIBRO MIXER" (manufactured by Chilling Industries Co., Ltd.)], 6) Ultrasonic impact type [e.g. ultrasonic homogenizer], 7) High pressure impact type [e.g. 8) Emulsification type [eg membrane emulsification module] and 9) Centrifugal thin film contact type [eg film mix].
Of these, 5), 8) and 9) are preferred.

(A) is further mixed with an aqueous medium containing a chain extender (f), a crosslinking agent (x) and / or a terminator (e2) as necessary, and reacted until the NCO group is substantially eliminated [water or ( It is obtained by performing chain extension according to f) and, if necessary, crosslinking by (x) and / or termination of reaction by (e2).
The temperature in mixing and reaction with the aqueous medium in this step is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 40 ° C.

  As (f) and (x), polyamine (k22) can be used. The amount of (f) and (x) used is preferably 0.2 to 2 equivalents of the primary and secondary amino groups of (f) and (x) with respect to 1 equivalent of the isocyanate group remaining in the prepolymer. More preferably, it is 0.3-1.2 equivalent.

As the terminator (e2), primary monoamine (k212), secondary monoamine (k214) and monohydric alcohol (e11) can be used.
The amount of (e2) used is preferably 0.5 equivalents or less, more preferably 0.03 to 0.3 equivalents per 1 equivalent of the NCO group of (A0). (E2) may be contained in an aqueous medium or may be added when the prepolymer is chain-extended.

  When chain extension by (f) and, if necessary, crosslinking by (x) and / or reaction termination by (e2) are performed, a continuous emulsifier [preferably 2 above, for example, Ebara Milder] is used (A0 ) Is dispersed in an aqueous medium, and then (f) and, if necessary, (x) and / or (e2) are added and mixed using a batch type emulsifier [preferably 1) vertical stirring method above ( A0) is preferably reacted.

  The solid content concentration (concentration of components other than the aqueous medium and the organic solvent) of (A) in (A1) is preferably 10 to 50%, more preferably 20 to 45%. The viscosity at 25 ° C. is preferably 1 to 500 mPa · s, more preferably 5 to 300 mPa · s. The viscosity can be measured using a B-type viscometer.

Further, the pH is preferably 6 to 10, more preferably 7 to 9, and the pH can be measured with pH Meter M-12 (manufactured by Horiba Seisakusho).

  The polyurethane resin aqueous dispersion (A1) is obtained by dispersing the polyurethane resin (A) in water, and the volume average particle diameter of the particles is preferably 10 to 200 nm, more preferably 20 to 150 nm.

[Acid-modified polyolefin (X)], [Acid-modified polyolefin aqueous dispersion (X1)]
The acid-modified polyolefin (X) can be used without any particular limitation, but may be a polyolefin obtained by modifying a polyolefin (D) having a double bond with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (B). preferable.
The polyolefin (D) having a double bond is preferably a thermal degradation product of the polyolefin (D0) from the viewpoint of having a double bond at the molecular end.

The polyolefin (D0) in the present invention includes one or more (co) polymers of olefins, and a copolymer of one or more olefins and one or more other monomers. A polymer is included.
Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter sometimes abbreviated as C) such as ethylene, propylene, 1- or 2-butene and isobutene, and C5-30 α-olefins (1-hexene). , 1-decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

  Specific examples of (D0) include ethylene unit-containing (propylene unit-free) copolymers such as high, medium and low density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1-butene etc. ), A copolymer with a C5-30 α-olefin (1-hexene, 1-dodecene, etc.) and vinyl acetate, etc. (weight ratio is the moldability of the polyolefin resin composition and the molecular end of (D) and / or From the viewpoint of the amount of double bonds in the molecular chain, preferably 30/70 to 99/1, more preferably 50/50 to 95/5) and the like; a propylene unit-containing (ethylene unit-free) copolymer such as polypropylene, Copolymer of propylene and C4-30 unsaturated monomer (same as above) (weight ratio is the same as above); ethylene / propylene copolymer (weight ratio is moldability of polyolefin resin composition) From the viewpoint of the amount of double bonds in the molecular ends and / or molecular chains of each (X), preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20/80); C4 or more Olefin (co) polymers such as polybutene.

  Of these, polyethylene, polypropylene, ethylene / propylene copolymer, propylene / C4-30 unsaturated monomer copolymer are preferable from an industrial viewpoint, and polyethylene, ethylene / propylene copolymer are more preferable. , An unsaturated monomer copolymer of propylene / C4-30. (D0) may be used alone or in combination of two or more.

  Weight average molecular weight of (D0) [hereinafter abbreviated as Mw. The measurement is performed by gel permeation chromatography (GPC) described later. same as below. ] Is preferably from 100,000 to 2,000,000, more preferably from 150,000 to 1,500,000, particularly preferably from the viewpoint of the mechanical strength of the molded product and the productivity of the polyolefin (D) described later. Is 200,000 to 1,000,000.

The measurement conditions of Mw and number average molecular weight (Mn) by GPC in the present invention are as follows.
Apparatus: High-temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Made by Polymer Laboratories, Inc.]
Column temperature: 135 ° C

In the polyolefin (D) having a double bond in the present invention, preferably, the polyolefin (D0) may be referred to as a thermal degradation method (hereinafter referred to as a thermal degradation method, for example, Japanese Patent Publication No. 43-9368, (Production method described in Japanese Patent Publication No. 44-29742 and Japanese Patent Publication No. 6-70094).
Moreover, as long as it has a double bond in a molecular terminal and / or molecular chain, you may use the polyolefin resin obtained by the polymerization method instead of thermal degradation.

  In the thermal degradation method, the polyolefin (D0) is subjected to (1) thermal degradation in the absence of an organic peroxide, preferably at 300 to 450 ° C. for 0.5 to 10 hours, and (2) organic peroxide. In the presence of a product [for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane], preferably at 180 to 300 ° C. for 0.5 to 10 hours.

(D) preferably has a double bond at the molecular end from the viewpoint of reactivity with an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (B) described later.
From the viewpoint of reactivity with (B), the number of double bonds of the molecule per 1,000 carbons (also referred to as 1,000 carbon atoms) of (D) is preferably 0.2 to 8, More preferably, it is 0.5-2.
Here, the number of double bonds can be determined from the spectrum of (D) ¹ H-NMR (nuclear magnetic resonance) spectroscopy.

  That is, the peak in the spectrum is assigned, and from the integral value derived from the double bond and the integral value derived from (D) at 4.5 to 6 ppm of (D), the number of double bonds (D) and (D) The relative value of the carbon number of (D) is calculated, and the number of double bonds of the molecule per 1,000 carbon atoms of (D) is calculated. The number of double bonds in the examples described later followed this method.

  The weight average molecular weight of (D) (hereinafter sometimes abbreviated as Mw) is 3,000 to 100,000, preferably 4,000 to 60,000. When the Mw is 3,000 or more, the coating film strength of the printed matter is good, and when the Mw is 100,000 or less, the viscosity is not high, and it is easy to synthesize (X) described later.

  The acid-modified polyolefin (X) is preferably a polyolefin obtained by modifying a polyolefin (D) having a double bond with an unsaturated polycarboxylic acid and / or an unsaturated carboxylic acid anhydride (B). The acid-modified polyolefin (X) can be obtained by reacting (D) and (B) in the presence or absence of the radical generator (C). (X) is preferably obtained in the absence of (C).

The unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (B) in the present invention is a C3-30 unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having one polymerizable unsaturated group. In addition, unsaturated carboxylic acid contains unsaturated monocarboxylic acid and / or unsaturated polycarboxylic acid.
Among these (B), as the unsaturated monocarboxylic acid, aliphatic (C3-24, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid and isocrotonic acid), alicyclic ring-containing (C6-24) Unsaturated poly (2-3 or more) carboxylic acids (anhydrides) include unsaturated dicarboxylic acids (anhydrides) [aliphatic dicarboxylic acids (anhydrides) (C4-24, For example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and anhydrides thereof), alicyclic dicarboxylic acid (anhydride) (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, Bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid and their anhydrides, and the like]. (B) may be used alone or in combination of two.
Of these, unsaturated dicarboxylic acid anhydride is preferable from the viewpoint of polymerizability with polyolefin (D), and maleic anhydride is more preferable.

  The acid-modified polyolefin (X) is preferably a polyolefin obtained by modifying a polyolefin (D) having a double bond with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (B), and more preferably of (D). It is a composition containing, as a main component, one having (B) added to one end or both ends.

  The acid-modified polyolefin (X) is a polyolefin (D) having a double bond to which (B) is not added, a polyolefin (B) having one molecule added to one end or one molecule added to both ends ( g1), polyolefin (g2) in which two or more molecules are copolymerized at one end or both ends, polymer (g3) in which only (B) is homopolymerized, and (B) remaining without being added It is a mixture. The acid value of (X) indicates the acid value of the above mixture.

In order to improve the water dispersibility of polyolefin, a form in which one molecule of (B) is added to one end of polyolefin (D) having a double bond, or one acid is added to both ends (above) (G1)) is most preferable.
Although it is a copolymer (above (g2)) in which two or more molecules of acid are connected to polyolefin, water dispersibility is better than that in which no acid is added (above (D)), (g1) Compared with, it does not contribute much to the improvement of water dispersibility, and the acid value of the mixture is unnecessarily increased, leading to deterioration of water resistance.
Therefore, for the purpose of satisfying both water dispersibility and water resistance, the composition of the above-mentioned acid-modified polyolefin (X) is mainly composed of (g1) and (D), (g2) and (g3) are minimized. Is effective.

In order to produce acid-modified polyolefin (X), polyolefin (D) having a double bond to which no acid is added and unsaturated polycarboxylic acid and / or unsaturated carboxylic acid anhydride (B) are heated and mixed. The addition reaction is generally performed.
Regarding the method of acid-modifying a polyolefin (D) having a double bond with an unsaturated polycarboxylic acid and / or an unsaturated carboxylic acid anhydride (B), (D) and (B) above the melting point of (D) May be heated and mixed.
At that time, a method of adding using a radical initiator (C) is common, but when adding using a radical initiator (C), (B) is easily self-polymerized, resulting in water dispersibility and The environment (B) that deteriorates water resistance is an environment in which a polyolefin (g2) copolymerized at one end or both ends, or a polymer (g3) in which only an acid is homopolymerized, is easily generated.

Therefore, it is preferable not to use the radical initiator (C), and even when it is used, it is preferable to keep it at 0.3% by weight or less based on the polyolefin (D).
Suppresses the formation of polyolefin (g2) in which acid is copolymerized at one or both ends and polymer (g3) in which only acid is homopolymerized, and acid is added to one end or one end to both ends As a condition for facilitating production of the polyolefin (g1), it is preferable not to use the radical initiator (C) as described above.

  In order to synthesize the acid-modified polyolefin (X), the polyolefin (D) and (B) containing a double bond under nitrogen flow without using 0.3 wt% or less of the radical initiator (C). ) Is most preferably heated and mixed. At this time, since (B) may be vaporized, it is preferable to flow hot water at a temperature at which (B) melts into the reflux pipe to reflux (B). The temperature at which (D) and (B) are mixed is not particularly limited as long as it is equal to or higher than the melting point of (D), but is preferably 160 ° C or higher and 220 ° C or lower, and is 180 ° C or higher and 210 ° C or lower. Particularly preferred. When the temperature is 160 ° C. or higher, the rate of addition reaction of (B) is fast, and when it is 220 ° C. or lower, the self-polymerization of (B) hardly occurs and water dispersibility and water resistance are good. Although there is no restriction | limiting in particular about the time which mixes (D) and (B), It is industrially preferable to keep within 30 hours.

  Since the unreacted remaining acid (x4) is easily vaporized, it can be easily removed under reduced pressure under heating. When (x4) is present, the water resistance deteriorates. Therefore, it is preferable to remove (x4) by heating (X) prepared by the above method to a temperature equal to or higher than the melting point and reducing the pressure.

The acid-modified polyolefin (X) in the present invention can be obtained by reacting the above (D) and (B) in the presence or absence of the radical initiator (C).
Examples of (C) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), etc.], peroxides [monofunctional (in the molecule (Having one peroxide group) (benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and polyfunctional (having two or more peroxide groups in the molecule) [2, 2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate and the like]] and the like.
Of these, from the viewpoint of the reactivity of (D) and (B), preferred are peroxides, more preferred are monofunctional peroxides, and particularly preferred are di-t-butyl peroxide, lauroyl peroxide and Dicumyl peroxide.

The amount of (C) used is preferably 10% or less, more preferably 3% or less, and particularly preferably 0.3% based on the total weight of (D) and (B) from the viewpoint of reactivity and side reaction suppression. %, And it is most preferable not to use the radical initiator (C).
The acid-modified polyolefin (X) produced by the above method can produce an aqueous dispersion having a lower acid value and better stability than the conventional one.

Specific methods for producing the acid-modified polyophine (X) of the present invention include the following methods [1] and [2].
[1] (D) and (B) are converted into a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (di-, tri- Or tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)]. If necessary, (C) [or a solution in which (C) is dissolved in an appropriate organic solvent (the same as above)], a chain transfer agent (t), and a polymerization inhibitor (f) described later are added. In addition, heating and stirring (solution method);
[2] A method (melting method) in which (D), (B) and, if necessary, (C), (t) and (f) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like.

  The reaction temperature in the solution method may be a temperature at which (D) is dissolved in an organic solvent, and is preferably 50 to 220 ° C., more preferably 110 to 210 ° C. from the viewpoint of the reactivity of (D) and (B). Especially preferably, it is 120-180 degreeC.

  The reaction temperature in the melting method may be a temperature at which (D) melts, and preferably 120 to 260 ° C. from the viewpoint of the reactivity of (D) and (B) and the decomposition temperature of the reaction product. Preferably it is 130-240 degreeC.

Examples of the chain transfer agent (t) include alcohols (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol and allyl alcohol); thiols (C1-24, such as ethylthiol, propiothiol, 1 -Or 2-butylthiol and 1-octylthiol, etc.); aldehydes (C2-18, such as 2-methyl-2-propylaldehyde, 1- or 2-butyraldehyde and 1-pentylaldehyde, etc.); phenols (C6-36) Amines (C3-24, such as diethylmethylamine, triethylamine, and diphenylamine); disulfides (C2-24, such as diethyl disulfide and di-1-propyl disulfide, etc.), for example, phenol, o-, m- or p-cresol ).
The amount of (t) used is preferably 30% or less based on the total weight of (D) and (B), and preferably 0.1 to 20% from the viewpoint of the reactivity of (D) and (B). .

Examples of the polymerization inhibitor (f) include catechol (C6-36, such as 2-methyl-2-propylcatechol), quinone (C6-24, such as p-benzoquinone), hydrazine (C2-36, such as 1, 3,5-triphenylhydrazine, etc.), nitro compounds (C3-24, such as nitrobenzene), stabilized radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 2,2 , 6,6-tetramethyl-1-piperidinyl oxide (TEMPO) and the like].
The amount of (f) used is preferably 5% or less based on the total weight of (D) and (B), and preferably 0.01 to 0 from the viewpoint of the stability and polymerizability of (D) and (B). .5%.

  The acid-modified polyolefin (X) in the present invention is obtained by the method for producing the acid-modified polyolefin (X).

  The weight ratio [(D) / (B)] between (D) and (B) in (X) is preferably 80/20 to 99.9 / 0. 1, more preferably 85/15 to 99.9 / 0.1.

The acid value of (X) is preferably 1 to 60 mg KOH / g (only numerical values are shown below), more preferably 4 to 40, and particularly preferably 6 from the viewpoint of dispersion stability of the aqueous dispersion (X1) described later. ~ 20.
The acid value here is a value obtained by measurement according to the following procedures (i) to (iii) according to JIS K0070.
(I) 1 g of (X) is dissolved in 100 g of xylene adjusted to 100 ° C.
(Ii) 0.1 mol / L potassium hydroxide ethanol solution [trade name “0.1 mol / L ethanolic potassium hydroxide solution”, manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator at the same temperature Perform titration.
(Iii) The amount of potassium hydroxide required for titration is converted to mg, and the acid value (unit: mgKOH / g) is calculated.
In the above measurement, one acid anhydride group is equivalent to one carboxyl group. The acid value in the examples described later was in accordance with this method.

  Mw of (X) is preferably from 20,000 to 120,000, more preferably from 30,000 to 110,000, still more preferably from 40,000 to 100,000, from the viewpoint of the mechanical strength of the coating film of the inkjet ink. 000.

The product [(acid value) × (weight average molecular weight)] of the acid value and the weight average molecular weight of (X) is preferably 20,000 to 7 from the viewpoint of the adhesive strength of the printed matter and the dispersion stability of (X). , 200,000, more preferably 160,000 to 2,000,000.
The number of (B) added or copolymerized to the acid-modified polyolefin (X) is 0.5 to 10 molecules on average as the total number of unsaturated carboxylic acid and unsaturated carboxylic anhydride per molecule (X). Preferably, there are 0.7 to 3 molecules, more preferably 1 to 2 molecules.
Water resistance is good when it is 10 molecules or less. Water dispersibility is good when the molecular weight is 0.5 or more. The method for obtaining the average number of (B) added or copolymerized with (X) per molecule is calculated from the acid value and the number average molecular weight (Mn) described above according to the following formula.
[(X) Average number of (B) per molecule]
= [Acid Value of (X)] x [Mn of (X)] / 56,100

  In the method for producing the aqueous dispersion (X1) of acid-modified polyolefin, first, the acid-modified polyolefin (X) is dissolved in a water-soluble organic solvent. At that time, heating is preferable because it can be dissolved quickly and uniformly. As the container, an apparatus widely known to those skilled in the art as a solid / liquid stirring apparatus or an emulsifier can be used, and an apparatus capable of pressurization of 0.1 MPa or more is preferably used. The stirring method and the rotation speed of the stirring are not particularly limited, but may be stirring at a low speed such that the resin is in a floating state in the aqueous medium. Therefore, high-speed stirring (for example, 1,000 rpm or more) is not essential, and an aqueous dispersion can be produced with a simple apparatus.

As the water-soluble organic solvent, those having a solubility in water at 20 ° C. of 50 g / L or more are preferably used, more preferably 100 g / L or more, and particularly preferably 200 g / L or more.
As the water-soluble organic solvent, those having a boiling point of 250 ° C. or lower are preferable, and those having a temperature of 50 to 200 ° C. are particularly preferable from the viewpoint of easy removal from the coating film. A water-soluble organic solvent having a boiling point exceeding 250 ° C. is difficult to be scattered from the resin coating film by drying, and the water resistance of the coating film and the adhesion to the substrate may deteriorate.
Specific examples of the water-soluble organic solvent used include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec- Alcohols such as amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone and cyclohexanone , Ethers such as tetrahydrofuran and dioxane, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-butyl, acetic acid-3-methoxybutyrate , Esters such as methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and ethylene glycol ethyl ether acetate Derivatives, further 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, acetoacetic acid Examples include ethyl, 1,2-dimethylglycerin, 1,3-dimethylglycerin, and trimethylglycerin.
These water-soluble organic solvents may be used as a mixture of two or more. Among these, at least one selected from the group consisting of ketones, ethers, and esters is preferable because the resin is easily dissolved.

  The solid content concentration of the acid-modified polyolefin (X) in the solution of the acid-modified polyolefin (X) is preferably 1 to 70%, more preferably 5 to 50%, and further preferably 10 to 40% from the viewpoint of workability. 10 to 35% is particularly preferable.

  Next, in the production method (X1) of the present invention, a basic compound is allowed to act on the acid group contained in the acid-modified polyolefin (X) to neutralize at least a part thereof. By reacting the basic compound, acid groups such as carboxyl groups and acid anhydride groups of the acid-modified polyolefin (X) are anionized, and the electrostatic repulsion of the anions prevents aggregation between the resin fine particles in the aqueous medium. And good dispersion is achieved.

Examples of the method of allowing the basic compound to act include 1) a method of adding together with a water-soluble organic solvent when the resin is dissolved, 2) a method of adding after the resin is dissolved, and 3) a method of adding as an aqueous solution after the resin is dissolved. .
The addition amount of the basic compound is preferably 0.3 to 3 times equivalent to the acid group (1 mol of acid anhydride group is regarded as 2 mol of carboxyl group) contained in the acid-modified polyolefin (X). 0.5 to 2 times equivalent is more preferable, and 0.6 to 1.5 times equivalent is particularly preferable. If it is 0.3 times equivalent or more, the addition effect of the basic compound is recognized, and if it is 3 times or less, the problem of odor of the dispersion and the drying time when forming a coating film or an adhesive layer are not prolonged.

  Examples of such basic compounds include sodium hydroxide, potassium hydroxide, organic amines, and ammonia, and are not particularly limited. However, ammonia or organic amine compounds that volatilize during the formation of the coating film are water resistance of the coating film, From the viewpoint of adhesiveness, an organic amine compound having a boiling point of 30 to 250 ° C, more preferably 50 to 200 ° C is preferable. When the boiling point is 30 ° C. or higher, the rate of volatilization when the resin is made into an aqueous solution, which will be described later, decreases, and the aqueous formation proceeds completely. When the boiling point is 250 ° C. or less, the organic amine compound can be scattered from the resin coating film by drying, and the water resistance and adhesiveness of the printed matter are good.

Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine.
Among these, at least one selected from the group consisting of triethylamine, N, N-dimethylethanolamine and N, N-diethylethanolamine is preferable. Two or more kinds may be used in combination.

Furthermore, in the manufacturing method of the aqueous dispersion (X1) of acid-modified polyolefin, the following manufacturing method which does not substantially use a surfactant is preferable from the viewpoint of printed matter properties, particularly adhesiveness.
Water is added to the water-soluble organic solvent solution of the neutralized acid-modified polyolefin (X) to form a W / O type dispersion, and then this is phase-shifted to the O / W type while adding water. . The temperature of water to be added is not particularly limited, but is preferably 10 to 90 ° C, and more preferably 30 to 70 ° C. Further, the addition rate of water is not particularly limited, but may be appropriately adjusted while observing the state in the system (the state of resin aggregation or precipitation). Further, the amount of water to be added is not particularly limited, but finally, the solid content of (X) is 1 to 50%, preferably 5 to 40%, more preferably 5 to 30%. Good.

  By the above-described method for producing the aqueous dispersion (X1), the acid-modified polyolefin (X) can be stably dispersed with a volume average particle size of 1 μm or less without substantially using a surfactant.

  “Substantially no surfactant” means that surfactants are not actively added to the system and consequently are not used. Although it is particularly preferable that the content of such a surfactant is zero, the surfactant may be contained in an amount of about 15% or less with respect to the acid-modified polyolefin (X) as long as the effects of the present invention are not impaired. There is no problem.

As the surfactant component in the present invention, those mentioned as the above-mentioned emulsifier (m) are used.
The volume average particle size of the acid-modified polyolefin (X) particles measured by a laser diffraction / scattering particle size distribution analyzer is 10 to 300 nm from the viewpoint of improving the dispersion stability of the aqueous resin composition for inkjet ink (Q). Preferably, 20 to 200 nm is more preferable.
The method for measuring the volume average particle size of the aqueous polyurethane resin dispersion (A1), the acid-modified polyolefin aqueous dispersion (X1), and the resin composition aqueous dispersion (Q) for inkjet ink described above is obtained by ionizing the aqueous dispersion. After diluting the resin to a solid content of 0.01% by weight, it can be measured using a light scattering particle size distribution analyzer [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

  In the method for producing the aqueous dispersion (X1), it is preferable from the viewpoint of finer and uniform particles that the obtained aqueous dispersion (X1) is further heated and stirred at 40 to 250 ° C. By adding this step, the aggregates and precipitates generated when water is added are refined and homogenized, and a good aqueous dispersion is obtained. Unnecessary substances such as undispersed matter are filtered from the aqueous dispersion. Filtering performance is greatly improved. Therefore, productivity is improved. When heating, it may be an open system or under reflux, but it is preferably carried out under pressure and in a closed system from the viewpoint of raising the temperature above the boiling point. The heating temperature is more preferably 60 to 200 ° C, still more preferably 80 to 190 ° C, and particularly preferably 100 to 180 ° C. When the temperature is less than 40 ° C., the effect of heating is small, and when it exceeds 250 ° C., the molecular weight of the acid-modified polyolefin (X) may be lowered. The heating and stirring time is preferably 0.1 to 24 hours, more preferably 0.2 to 5 hours. If it is less than 0.1 hour, the effect of heating is small, and if it exceeds 24 hours, the molecular weight of the acid-modified polyolefin (X) may be lowered. As a heating method in the tank, heating from the outside of the tank is preferable. For example, the tank can be heated using oil or water, or a heater can be attached to the tank for heating.

  In the method for producing the aqueous dispersion (X1), a part of the water-soluble organic solvent contained therein is stripped from the obtained aqueous dispersion including the aqueous dispersion after heating and stirring. It is preferable to distill out of the system by a solvent removal operation called. By this operation, the amount of the water-soluble organic solvent in the aqueous dispersion may be appropriately reduced within the above range, or may be 10% or less. The following is more preferable.

Distilling off the water-soluble organic solvent by stripping requires measures in the production process such as increasing the pressure reduction of the equipment or extending the operation time. Is about 0.01% (the detection limit of the analytical instrument used for the measurement of the present invention). However, even if it is less than 0.01%, the performance as an aqueous dispersion is not particularly problematic. Even if the amount of the water-soluble organic solvent is reduced by stripping, the aqueous dispersion obtained by the production method of the present invention is not particularly affected in terms of performance and can be used favorably for various applications.

  Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring at normal pressure or reduced pressure to distill off the organic solvent. The organic solvent content can be quantified by gas chromatography. Further, since the concentration of the acid-modified polyolefin (X) is increased by distilling off the aqueous medium, for example, when the viscosity increases and the workability deteriorates, water is previously added to the aqueous dispersion. It can also be added.

  The resin content of the aqueous dispersion (X1) obtained by the production method of the present invention is appropriately adjusted depending on the film forming conditions, the desired thickness and performance of the resin layer, and is not particularly limited. 1 to 50% is preferable, 3 to 50% is more preferable, 5 to 45% is still more preferable, and 5 to 40% is particularly preferable.

[Aqueous Resin Composition for Inkjet Ink Dispersion (Q)]
The resin composition aqueous dispersion (Q) for inkjet ink of the present invention is obtained by mixing the aqueous dispersion (A1) of the polyurethane resin (A) and the aqueous dispersion (X1) of the acid-modified polyolefin (X). It is also possible to obtain a mixture of the polyurethane resin (A) and the acid-modified polyolefin (X) as an aqueous dispersion.
(Q) is an aqueous dispersion (A1) of polyurethane resin (A) and an aqueous dispersion (X1) of acid-modified polyolefin (X) from the viewpoints of adhesion to nonpolar substrates such as polyolefin resins and scratch resistance. It is preferable to obtain by mixing.

In the aqueous dispersion (Q) of the present invention, the weight ratio [(A) :( X)] of the polyurethane resin (A) and the acid-modified polyolefin (X) is determined by adhesion to a nonpolar substrate such as a polyolefin resin and the like. From the viewpoint of scratch resistance, it is preferably 5:95 to 95: 5, more preferably 30:70 to 90:10, still more preferably 45:55 to 85:15, and particularly preferably 60:40 to 80:20. It is.
When (A) :( X) is 30:70 to 90:10, adhesion to a polar substrate such as a PET film or a nylon film is good. Further, when (A) :( X) is 10:90 to 45:55, the blocking resistance to a substrate such as paper to be printed becomes good.

Hereinafter, a method for producing the aqueous resin composition dispersion (Q) for an inkjet ink of the present invention and preparation of an inkjet ink (J) using (Q) will be described.
The inkjet ink (J) contains a pigment (P) and a moisture retention stabilizing aid (M) in addition to the aqueous resin composition dispersion (Q) for inkjet ink of the present invention.

The solid content of the resin composition aqueous dispersion (Q) of the present invention, that is, the content of the total amount of the polyurethane resin (A) and the acid-modified polyolefin (X) is preferably 10 to 10 based on the weight of (Q). 60% by weight, more preferably 20-50% by weight.
As for the solid content of the aqueous dispersion (Q), about 1 g of the aqueous dispersion was thinly spread on a Petri dish, precisely weighed, and then the weight after heating at 130 ° C. for 45 minutes using a circulating constant temperature dryer was precisely adjusted. It can be obtained by weighing and calculating the ratio (percentage) of the remaining weight after heating to the weight before heating.
The solid content of the aqueous polyurethane resin dispersion (A1) and the acid-modified polyolefin resin aqueous dispersion (X1) can also be measured in the same manner as in (Q).

  The content of the aqueous resin composition for inkjet ink dispersion (Q) is preferably 1 to 90% by weight, more preferably 5 to 50% based on the weight of the inkjet ink (J). The content of the pigment (P) is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the inkjet ink. The content of the moisture retention stabilizing aid (M) is preferably 0.1 to 90% by weight, more preferably 1 to 50% by weight, based on the weight of the inkjet ink (J).

  Examples of the pigment (P) include inorganic pigments having a solubility in water of 1 or less (for example, white pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, purple pigment and metallic pigment) Organic pigments (for example, natural organic pigments, synthetic organic pigments, nitroso pigments, nitro pigments, pigment dye-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes) Xanthane lake, anthraquinone lake, pigments from vat dyes, and phthalocyanine pigments).

  The moisturizing and stabilizing aid (M) is not particularly limited, but is preferably a compound having a hydroxyl group and having a boiling point of 100 ° C. or higher. Examples include glycerin, propylene glycol, ethylene glycol, 1,3-propanediol, and triethylene glycol monobutyl ether.

  In the inkjet ink (J), the polyurethane resin (A), acid-modified polyolefin (X), pigment (P) and moisturizing stabilizing aid (for the present invention) may be added to the ink jet ink (J) as necessary for the purpose of assisting in forming a coating film and improving the binder function. In addition to M), other aqueous medium-dispersible resins or water-soluble resins may be used in combination as long as performance such as adhesion and dispersion stability is not impaired. The total content of the other aqueous medium-dispersible resin and the water-soluble resin is preferably 20% by weight or less based on the weight of the inkjet ink (J).

  Examples of other aqueous medium-dispersible resins or water-soluble resins used in combination with the inkjet ink (J) include aqueous medium-dispersible or water-soluble polyurethane resins other than the polyurethane resin in the present invention, polyacrylic resins, and polyester resins. Can be mentioned.

  The inkjet ink (J) can further contain one or more of a viscosity modifier, an antifoaming agent, an antiseptic, a deterioration preventing agent, a stabilizer, an antifreezing agent and water.

Viscosity modifiers include thickeners such as inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose viscosity modifiers (such as methylcellulose, carboxymethylcellulose, and hydroxymethylcellulose with Mn of 20,000 or more), proteins System viscosity modifiers (casein, casein soda, casein ammonium, etc.), acrylics (such as sodium polyacrylate and ammonium polyacrylate with Mn of 20,000 or more) and vinyl viscosity modifiers (Mn of 20,000 or more) Polyvinyl alcohol).
Examples of antifoaming agents include long-chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), and silicone oils (such as polymethylsiloxane and polyether-modified silicone).

Examples of the preservative include organic nitrogen sulfur compound preservatives and organic sulfur halide preservatives.
Deterioration inhibitors and stabilizers (such as UV absorbers and antioxidants) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based and benzotriazole-based deterioration inhibitors and stabilizers. .
Examples of the antifreezing agent include ethylene glycol and propylene glycol.
The contents of the viscosity modifier, antifoaming agent, antiseptic, deterioration preventing agent, stabilizer and antifreezing agent are each preferably 5% by weight or less, more preferably 3 based on the weight of the inkjet ink (J). % By weight or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Hereinafter, the part means part by weight.

<Manufacture example 1><Manufacture of the aqueous dispersion (A1-1) of (A-1)>
In a reaction vessel equipped with a stirrer and a heating device, 447.0 parts of polycarbonate diol ("Duranol G4672" manufactured by Asahi Kasei Chemicals) with Mn of 2,000, 1.1 parts of 1,4-butanediol, 2,2-di 57.4 parts of methylolpropionic acid, 1.5 parts of hindered phenolic antioxidant ("Irganox 245" manufactured by BASF Japan), 263.0 parts of 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 330 parts of acetone The reaction system was replaced with nitrogen gas, and reacted at 92 to 98 ° C. for 10 hours with stirring to obtain a terminal isocyanate group urethane prepolymer. The obtained acetone solution was cooled to 50 ° C. or lower, and 108 parts of acetone, 2.3 parts of an ultraviolet absorber (“TINUVIN 144” manufactured by BASF Japan), and 43.3 parts of triethylamine were added. After adding 1155 parts of water to the acetone solution and emulsifying by stirring for 1 minute with a homomixer, the acetone was distilled off under reduced pressure. After cooling to room temperature, water was added to the aqueous dispersion of polyurethane resin (A-1) (A1-1) was obtained. The aqueous dispersion (A1-1) had a solid content concentration of 40.3% by weight and a volume average particle size of 93 nm.

<Production Example 2><Production of aqueous dispersion (X1-1) of acid-modified polyolefin (X-1)>
A reactor was charged with 100 parts of polyolefin (D0-1) having an Mw of 200,000 having propylene 70 mol% and 1-butene 30 mol% as structural units, and heated with a mantle heater while nitrogen was bubbled through the gas phase. While melted, it was subjected to thermal degradation at 360 ° C. for 70 minutes with stirring to obtain a polyolefin (D-1) having a double bond. In (D-1), Mw 8,000, the number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms was 7.4. Subsequently, 100 parts of (D-1) and 4 parts of maleic anhydride (B-1) were charged in a reaction vessel, and after nitrogen substitution, the mixture was heated to 180 ° C. under nitrogen flow to be uniformly dissolved. A solution prepared by dissolving 1 part of dicumyl peroxide [manufactured by NOF "PARK Mill D"] (C-1) in 10 parts of xylene was added dropwise over 10 minutes, and stirring was continued for 3 hours under reflux of xylene. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain acid-modified polyolefin (X-1). The acid value of the acid-modified polyolefin (X-1) was 21, and the Mw was 50,000. (D-1) The average (B-1) added per molecule was 5.6 molecules.

Furthermore, 48.0 parts of acid-modified polyolefin (X-1), 128.0 parts of tetrahydrofuran, 4.0 parts of N, N-dimethylethanolamine was charged and the system temperature was 60 ° C. to dissolve the resin.
After cooling to 30 ° C. by air cooling and adding 144 parts of water over about 5 minutes, the system was further sealed and stirred at 110 ° C. for 1 hour. Then, it cooled to room temperature (about 25 degreeC), stirring by air cooling. 200 parts of the obtained aqueous dispersion and 38 parts of distilled water were charged into a 1 L two-necked round bottom flask, a mechanical stirrer and a Liebig condenser were installed, the flask was heated in an oil bath, and the aqueous medium was distilled off. . When about 110 parts of the aqueous medium was distilled off, heating was terminated and the mixture was cooled to room temperature.
After cooling, the liquid component in the flask was subjected to pressure filtration (air pressure 0.2 MPa) with a 600 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the solid content concentration of the filtrate was measured to find 25.4 mass. %Met. While stirring the filtrate, distilled water was added to adjust the solid content concentration to 25.0% by mass. The aqueous dispersion (X1-1) of the acid-modified polyolefin (X-1) had a solid content concentration of 25.0% by weight and a volume average particle size of 154 nm.

<Production Example 3><Production of aqueous dispersion (X1-2) of acid-modified polyolefin (X-2)>
A reactor was charged with 100 parts of polyolefin (D0-1) having an Mw of 200,000 having propylene 70 mol% and 1-butene 30 mol% as structural units, and heated with a mantle heater while nitrogen was bubbled through the gas phase. While melted, it was subjected to thermal degradation at 330 ° C. for 80 minutes with stirring to obtain polyolefin (D-2). In (D-2), Mw was 50,000, the number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms was 1.1. Subsequently, 100 parts of (D-2) and 0.8 part of maleic anhydride (B-1) were charged into the reaction vessel, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen flow to dissolve uniformly. . A solution prepared by dissolving 0.1 part of (C-1) in 10 parts of xylene was added dropwise over 10 minutes, and stirring was continued for 3 hours under reflux of xylene. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain acid-modified polyolefin (X-2). The acid value of acid-modified polyolefin (X-2) was 5, and Mw was 62,000. (D-2) The average (B-1) added per molecule was 2 molecules.
Furthermore, 100 parts of (X-2), 1.5 parts of N, N-dimethylethanolamine and 80 parts of tetrahydrofuran were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, and the temperature was adjusted to 60 ° C. with stirring. And dissolved uniformly. 233 parts of water was added little by little over 5 hours to carry out phase inversion emulsification. After cooling to room temperature, tetrahydrofuran was removed under reduced pressure, and water was added so that the solid content was 25.0% by weight. The aqueous dispersion (X1-2) of the acid-modified polyolefin (X-2) had a solid content concentration of 25.0% by weight and a volume average particle size of 220 nm.

<Production Example 4><Production of aqueous dispersion (X1-3) of acid-modified polyolefin (X-3)>
100 parts of (D-2) obtained in Production Example 3 and 3.2 parts of maleic anhydride (B-1) were charged into a reaction vessel, and after nitrogen substitution, the temperature was raised to 200 ° C. under nitrogen flow. After stirring at 200 ° C. for 15 hours, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain acid-modified polyolefin (X-3). The acid value of acid-modified polyolefin (X-3) was 5, and Mw was 60,000. (D-2) The average (B-1) added per molecule was 1.8 molecules.
Further, 100 parts of (X-3), 1.5 parts of N, N-dimethylethanolamine and 80 parts of tetrahydrofuran were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, and the temperature was adjusted to 60 ° C. with stirring. And dissolved uniformly. 233 parts of water was added little by little over 5 hours to carry out phase inversion emulsification. After cooling to room temperature, tetrahydrofuran was removed under reduced pressure, and water was added so that the solid content was 25.0%. The solid content concentration of the aqueous dispersion (X1-3) of the acid-modified polyolefin (X-3) was 25.0% by weight, and the volume average particle diameter was 223 nm.

<Production Example 5><Production of aqueous dispersion (X1-4) of acid-modified polyolefin (X-3)>
100 parts of (X-3) obtained in Production Example 4, 1.5 parts of N, N-dimethylethanolamine, 8 parts of an EO adduct of higher alcohol [“Emalmine 50” manufactured by Sanyo Chemical Industries], and 80 parts of tetrahydrofuran A reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged, and the temperature was adjusted to 60 ° C. with stirring to dissolve uniformly. 233 parts of water was added little by little over 5 hours to carry out phase inversion emulsification. After cooling to room temperature, tetrahydrofuran was removed under reduced pressure, and water was added so that the solid content was 25.0%. The solid content concentration of the aqueous dispersion (X1-4) of the acid-modified polyolefin (X-3) was 25.0% by weight, and the volume average particle size was 150 nm.

<Production Example 6><Production of aqueous dispersion (X1-5) of acid-modified polyolefin (X-4)>
A reactor was charged with 100 parts of polyolefin (D0-1) having an Mw of 200,000 having propylene 70 mol% and 1-butene 30 mol% as structural units, and heated with a mantle heater while nitrogen was bubbled through the gas phase. While melted, it was subjected to thermal degradation at 360 ° C. for 20 minutes with stirring to obtain polyolefin (D-3). In (D-3), Mw 140,000, the number of double bonds in the molecular terminal and / or molecular chain per 1,000 carbon atoms was 1.5.
Subsequently, 100 parts of (D-3) and 4 parts of maleic anhydride (B-1) were charged in a reaction vessel, and after nitrogen substitution, the mixture was heated to 180 ° C. under nitrogen flow to be uniformly dissolved. A solution prepared by dissolving 1 part of (C-1) in 10 parts of xylene was added dropwise over 10 minutes, and stirring was continued for 3 hours under reflux of xylene. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain acid-modified polyolefin (X-4). The acid value of the acid-modified polyolefin (X-4) was 21, and the Mw was 670,000. (D-3) The average (B-1) added per molecule was 75 molecules.

Furthermore, 48.0 parts of acid-modified polyolefin (X-4), 128.0 parts of tetrahydrofuran, 4.0 parts of N, After charging N-dimethylethanolamine and dissolving the resin at a system temperature of 60 ° C., 5 parts of polyoxyethylene nonylphenyl ether (“Nonion NS-208.5” manufactured by NOF) was added as a surfactant. It was.
After cooling to 30 ° C. by air cooling and adding 144 parts of water over about 5 minutes, the system was further sealed and stirred at 110 ° C. for 1 hour. Then, it cooled to room temperature (about 25 degreeC), stirring by air cooling. 200 parts of the obtained aqueous dispersion and 38 parts of distilled water were charged into a 1 L two-necked round bottom flask, a mechanical stirrer and a Liebig condenser were installed, the flask was heated in an oil bath, and the aqueous medium was distilled off. . When about 110 parts of the aqueous medium was distilled off, heating was terminated and the mixture was cooled to room temperature.
After cooling, the liquid component in the flask was subjected to pressure filtration (air pressure 0.2 MPa) with a 600 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the solid content concentration of the filtrate was measured to be 25.7 mass. %Met. While stirring this filtrate, distilled water was added to adjust the solid content concentration to 25.0% by mass, and an aqueous dispersion (X1-5) containing acid-modified polyolefin (X-4) and a surfactant was added. ) The solid content concentration of (X1-5) was 25.0% by weight, and the volume average particle size was 158 nm.

<Manufacture example 7><Manufacture of the aqueous dispersion (A1-2) of (A-2)>
In a reaction vessel equipped with a stirrer and a heating device, 438.8 parts of polycaprolactone diol ("Placcel CL220" manufactured by Daicel) with Mn of 2,000, 26.1 parts of 1,4-butanediol, 2,2-di 36.8 parts of methylolpropionic acid, 1.5 parts of hindered phenolic antioxidant ("Irganox 245" manufactured by BASF Japan), 266.8 parts of 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 330 parts of acetone The reaction system was replaced with nitrogen gas, and reacted at 92 to 98 ° C. for 10 hours with stirring to obtain a terminal isocyanate group urethane prepolymer. The obtained acetone solution was cooled to 50 ° C. or lower, and 108 parts of acetone, 2.3 parts of an ultraviolet absorber (“TINUVIN 144” manufactured by BASF Japan), and 27.6 parts of triethylamine were added. 1155 parts of water is added to the acetone solution and emulsified by stirring for 1 minute with a homomixer, then 33.1 parts of a 10 wt% aqueous solution of ethylenediamine is added, the acetone is distilled off under reduced pressure, and after cooling to room temperature, water is added. An aqueous dispersion (A1-2) of polyurethane resin (A-2) was obtained. The solid content concentration of the aqueous dispersion (A1-2) was 40.3% by weight, and the volume average particle size was 100 nm.

<Production Example 8><Production of aqueous dispersion (A1-3) of (A-3)>
In a reaction vessel equipped with a stirrer and a heating device, 379.9 parts of polytetramethylene ether glycol ("PTMG 2000" manufactured by Mitsubishi Chemical) with Mn of 2,000, 40.5 parts of 1,4-butanediol, 2, 2-dimethylolpropionic acid 36.8 parts, hindered phenolic antioxidant ("Irganox 245" manufactured by BASF Japan) 1.5 parts, 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI) 311.3 parts and After charging 330 parts of acetone and replacing the reaction system with nitrogen gas, the reaction was carried out at 92 to 98 ° C. for 10 hours with stirring to obtain a terminal isocyanate group urethane prepolymer. The obtained acetone solution was cooled to 50 ° C. or lower, and 108 parts of acetone, 2.3 parts of an ultraviolet absorber (“TINUVIN 144” manufactured by BASF Japan), and 27.6 parts of triethylamine were added. 1155 parts of water is added to the acetone solution and emulsified by stirring with a homomixer for 1 minute, and then 46.2 parts of a 10% by weight aqueous solution of diethylenetriamine is added. Acetone is distilled off under reduced pressure. After cooling to room temperature, water is added. An aqueous dispersion (A1-3) of a polyurethane resin (A-3) was obtained. The aqueous dispersion (A1-3) had a solid content concentration of 40.3% by weight and a volume average particle size of 90 nm.

<Production Example 9><Aqueous dispersion (A1-4) of polyurethane resin (A-4)>
In a reaction vessel equipped with a stirrer and a heating device, 534.8 parts of polytetramethylene ether glycol (“PTMG 2000” manufactured by Mitsubishi Chemical) having a Mn of 2,000, 37.2 parts of 1,4-butanediol, hindered After charging 1.5 parts of a phenolic antioxidant ("Irganox 245" manufactured by BASF Japan), 196.4 parts of isophorone diisocyanate (IPDI), and 330 parts of acetone, and substituting the reaction system with nitrogen gas, the mixture was stirred under 92 ~ It was made to react at 98 degreeC for 10 hours, and the terminal isocyanate group urethane prepolymer was obtained.
The obtained acetone solution was cooled to 50 ° C. or lower, and 108 parts of acetone, 2.3 parts of an ultraviolet absorber (“Irganox 245” manufactured by BASF Japan), polyoxyalkylene alkyl ether as an emulsifier (manufactured by Sanyo Chemical Industries “ Narrow Acty CL120 ") 115.5 parts. After adding 1155 parts of water to the acetone solution and emulsifying by stirring for 1 minute with a homomixer, the acetone was distilled off under reduced pressure, and after cooling to room temperature, water was added and a polyurethane resin for comparative example (A-4 ) Aqueous dispersion (A1-4) was obtained. The solid content concentration of the aqueous dispersion (A1-4) was 40.3% by weight, and the volume average particle size was 350 nm.

<Example 1>
100 parts of the aqueous dispersion (A1-1) obtained in Production Example 1 and 69 parts of the aqueous dispersion (X1-1) obtained in Production Example 2 are mixed, and the polyurethane resin (A-1) and the acid-modified polyolefin are mixed. The weight ratio of (X-1) was adjusted to 70:30. Then, it diluted using 23 parts of ion-exchange water, and obtained the resin composition aqueous dispersion (Q-1) for inkjet inks of solid content concentration of 30 weight%. The volume average particle diameter was 134 nm.

<Examples 2-9 and Comparative Examples 1-2>
In the same manner as in Example 1, the parts of the aqueous dispersions (A1-1) to (A1-4) and aqueous dispersions (X1-1) to (X1-5) described in Table 1 are optionally ion-exchanged water. Were used to obtain aqueous resin composition dispersions (Q-2) to (Q-9) and (Q′-1) to (Q′-2). Table 1 shows the volume average particle diameter.

<Examples 10 to 18 and Comparative Examples 3 to 4>
Using the aqueous ink dispersions (Q-1) to (Q-9) obtained in Examples 1 to 9, the carbon black water dispersion [[ Aqua-Black162 ”, manufactured by Tokai Carbon Co., Ltd., solid content 20 wt%], and propylene glycol and glycerin as a moisturizing stabilizing aid (M) were blended, and inkjet inks (J-1) to (J-89) and ( J'-1) to (J'-2) were obtained.

  Table 2 shows the evaluation results of the inkjet inks (J-1) to (J-8) and (J′-1) to (J′-3) obtained in Examples 10 to 18 and Comparative Examples 3 to 4. . In addition, the evaluation method in this invention is as follows.

<Dispersion stability of resin composition aqueous dispersion (Q)>
The polyurethane resin aqueous dispersion whose temperature was adjusted to 40 ° C. was allowed to stand for 7 days, and the occurrence of sediment was visually evaluated.
The case where no sediment was generated was marked as ◯, and the case where sediment was generated was marked as x.

<Image adhesion>
The produced ink-jet inks (J-1) to (J-9) and (J′-1) to (J′-2) are 5 cm × 20 cm PP synthetic paper “Super Yupo FRB110 manufactured by Yupo Corporation”. The film was coated with a bar coater so that the film thickness after drying was 2 μm, and heated at 100 ° C. for 10 minutes to produce a printed matter. A cross-cut peel test using a cloth adhesive tape (trade name: 123LW-50, manufactured by Nichiban Co., Ltd.) was performed on this coating film, and the number of remaining squares of 100 test squares was counted.

<Abrasion resistance>
The film thickness after drying the produced inkjet inks (J-1) to (J-9) and (J'-1) to (J'-2) on a PP film substrate to a PP film of 5 cm x 10 cm is 2 m. Then, it was applied with a bar coater and heated at 80 ° C. for 10 minutes to produce a printed matter. The prepared coating film was subjected to 50 reciprocations with a dry cotton (Kanakin No. 3) using a Gakushin type friction tester under a load of 200 g, and then visually evaluated according to the following criteria.

A: The image density on the printed surface does not change, and the color does not transfer to cotton.
○: No change in the image density on the printed surface is observed, but a slight color transfer is observed in cotton.
(Triangle | delta): The image density of a printing surface falls.
X: The ink on the printing surface is peeled off.

<Blocking resistance>
After drying the prepared inkjet inks (J-1) to (J-9) and (J′-1) to (J′-2) on a 5 cm × 20 cm OK top coat mat (manufactured by Oji Paper Co., Ltd.) The film was coated with a bar coater so that the film thickness was 2 μm, and heated at 100 ° C. for 10 minutes to produce a printed matter. An uncoated OK top coat mat was placed on this coating film, and left in an oven at 40 ° C. for 24 hours while applying a load of 1 kg / cm ² using a blocking tester. Then, the test sample was taken out and the overlapped OK top coat mat was peeled off. The color transfer to the peeled off OK top coat mat was visually evaluated according to the following evaluation criteria.

A: No color transfer and no resistance during peeling.
○: The color does not transfer, but there is some resistance during peeling.
(Triangle | delta): There is some color transfer and there exists some resistance at the time of peeling.
X: There is color transfer and there is resistance during peeling.

  As shown in Table 2, the inkjet inks (J-1) to (J-9) of the present invention described in the examples are the same as the inkjet inks (J′-1) to (J′-2) of the comparative examples. It can be seen that the image adhesion and scratch resistance are superior. Moreover, the inkjet ink (J-5) of this invention is excellent in blocking resistance, maintaining abrasion resistance.

  The printing method using the aqueous resin composition for inkjet ink of the present invention is not particularly limited, and examples thereof include home printing, business printing, sign graphic printing, and pigment textile printing. Particularly preferred are sign graphic printing and pigment textile printing.

Claims (11)

  A resin composition aqueous dispersion (Q) for inkjet ink containing a polyurethane resin (A), an acid-modified polyolefin (X) and an aqueous medium.   The aqueous dispersion according to claim 1, wherein the polyurethane resin (A) is dispersed in an aqueous medium, and the acid-modified polyolefin (X) is dispersed in the aqueous medium.   The aqueous dispersion according to claim 1 or 2, wherein the weight ratio [(A) :( X)] of the polyurethane resin (A) and the acid-modified polyolefin (X) is 5:95 to 95: 5.   The acid-modified polyolefin (X) is a polyolefin obtained by modifying a polyolefin (D) having a double bond with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (B). Aqueous dispersion.   The aqueous dispersion according to claim 4, wherein the polyolefin (D) having a double bond is a thermal degradation product of the polyolefin (D0).   The aqueous dispersion according to claim 4 or 5, wherein the polyolefin (D) having a double bond is a polyolefin having 0.2 to 8 double bonds per 1,000 carbon atoms.   The aqueous dispersion according to any one of claims 1 to 6, wherein the acid-modified polyolefin (X) has an acid value of 1 to 60 mgKOH / g and a weight average molecular weight of 20,000 to 120,000.   The acid-modified polyolefin (X) is an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride with respect to one molecule of the polyolefin (D) containing a double bond. The aqueous dispersion according to any one of claims 1 to 7, wherein 1 to 2 molecules are added on average as the total number of molecules of the product. The polyurethane resin (A) has a polyisocyanate (a), a polyol (b), a carboxylic acid (salt) group (α) or a sulfonic acid (salt) group (β) in the molecule, and further in the molecule. The aqueous dispersion according to any one of claims 1 to 8, which is a polyurethane resin comprising a compound (d) having two or more active hydrogen atom-containing groups as an essential constituent raw material.   The aqueous dispersion according to any one of claims 1 to 9, wherein the polyol (b) is a polycarbonate polyol (b113).   The inkjet ink (J) containing the resin composition aqueous dispersion (Q) of any one of Claims 1-10, a pigment (P), and a moisturizing stabilization aid (M).