JP2018178090A - Polyurethane resin composition aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin composition aqueous dispersion excellent in adhesiveness with a substrate and film strength.SOLUTION: There is provided a polyurethane resin composition aqueous dispersion containing a polyurethane resin (U) having a functional group (f) which is one or more kind of group selected from a carboxyl group, a carboxylate anion group and a hydroxyl group, a crosslinking agent (T) having 2 or more 1 or more kind of functional group selected from a carbodiimide group (t1), an oxazoline group (t2), an epoxy group (t3) and a silanol group (t4) in a molecule, a blocked polyisocyanate compound (J) and an aqueous medium, in which the polyisocyanate compound (J) is a reaction product between polyisocyanate compound (I) having a functional group (g) which is one or more kind of group selected from the carboxyl group, the carboxylate anion group and the hydroxyl group and an isocyanate blocking agent (E).SELECTED DRAWING: None

Description

  The present invention relates to a polyurethane resin composition aqueous dispersion.

Polyurethane resins have been conventionally used in paints, adhesives, fiber processing agents, paper processing agents, inks and the like because they have excellent flexibility, adhesion, chemical resistance, film strength and abrasion resistance. From the viewpoint of improving adhesion, a method of introducing a blocked isocyanate group into a urethane resin composition has been proposed, and is used to improve adhesion to a substrate having active hydrogen groups such as hydroxyl groups on the surface of materials such as metals, fibers, and paper. It is done.
As a method of introducing a block isocyanate group into a polyurethane resin aqueous dispersion, for example, a polyurethane resin aqueous dispersion is disclosed, which is prepared by synthesizing a polyurethane resin having an isocyanate group terminal, blocking the terminal isocyanate group and then emulsifying and dispersing it. (Refer patent documents 1-3). However, since the polyurethane resin aqueous dispersion described in Patent Document 1 introduces a block isocyanate group at the end, if the content of the block isocyanate group is increased to improve the adhesion, the molecular weight of the urethane resin decreases and the film strength There is a problem that the decrease is remarkable, and it is difficult to achieve both adhesion and film strength. Also, as a method for achieving both adhesion and film strength, the particles of the highly crosslinkable polyurethane resin aqueous dispersion have nonionic polar groups. The polyurethane resin composition aqueous dispersion which included the block isocyanate compound which it has is disclosed (refer patent document 4). In a resin composition containing a polyurethane resin and a block isocyanate compound as described in Patent Document 4, in order to sufficiently develop the adhesion to the substrate and the film strength, the isocyanate group generated by the deblocking by heating is a substrate It is necessary to react with the active hydrogen groups present in the polyurethane resin and also with the active hydrogen groups present in the polyurethane resin. However, the polyurethane resin composition aqueous dispersion described in Patent Document 4 has only an active hydrogen group having low reactivity such as a urethane group and a urea group as an active hydrogen group capable of reacting with an isocyanate group. In particular, there has been a problem that the adhesion to the substrate and the film strength become insufficient under low temperature baking conditions.

International Publication WO 2010-098316 International Publication WO 2010-098317 International Publication WO 2010-098318 Patent No. 5170499 gazette

  An object of the present invention is to provide a polyurethane resin composition aqueous dispersion which is excellent in adhesion to a substrate and film strength.

The present inventors arrived at the present invention as a result of intensive studies to achieve the above object.
That is, the present invention provides a polyurethane resin (U) having at least one functional group (f) selected from a carboxyl group, a carboxylate anion group and a hydroxyl group, a carbodiimide group (t1), an oxazoline group (t2) and an epoxy group (t3). A polyurethane resin composition aqueous dispersion containing a crosslinking agent (T) having two or more functional groups of at least 2 selected from the group consisting of silanol groups (t4) and a blocked polyisocyanate compound (J) and an aqueous medium Polyisocyanate Compound (I) and Isocyanate Blocking Agent Having a Functional Group (g) and a Polyisocyanate Compound (J) and at least one Group of a Carboxyl Group, a Carboxylate Anion Group, and a Hydroxyl Group Polyurethane resin composition aqueous dispersion (Q) which is a reaction product with (E); the polyurethane It is an inkjet ink (L) containing a resin composition aqueous dispersion (Q), a pigment, and a moisturizing stabilization aid.

  The dry film of the polyurethane resin composition aqueous dispersion of the present invention has excellent adhesion to a substrate and film strength.

<Polyurethane resin (U)>
As the functional group (f) having reactivity with the carbodiimide group (t1), the oxazoline group (t2), the epoxy group (t3) and the silanol group (t4) in the crosslinking agent (T) in the present invention, carboxyl group and / Or carboxylate anion groups (f1) and hydroxyl groups (f2).
In the case of (f1), the polyurethane resin (U) having (f1) is a compound (c) containing a carboxyl group and / or a carboxylate anion group (f1) and two active hydrogen atoms as its constituent monomer And polyurethane resins (U) having

  As the compound (c) containing (f1) and two active hydrogen atoms, for example, a compound having a carboxyl group and having 2 to 10 carbon atoms [dialkylolalkanoic acid (for example, 2,2-dimethylolpropionyl Acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid), tartaric acid and amino acids (eg, glycine, alanine and valine), etc. and the like; The salt neutralized with a Japanese chemical agent is mentioned.

As a neutralizing agent used for the salt of (c), ammonia, a C1-C20 amine compound, or alkali metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide etc.) are mentioned, for example.
Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, dimethylamine, diethylamine, dibutylamine, diethanolamine and diisopropanolamine, and secondary ones such as methylpropanolamine Examples thereof include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

  The neutralizing agent used for the salt of (c) may use only 1 type, and may use 2 or more types together.

  As the neutralizing agent used for the salt of (c), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the resulting polyurethane resin composition aqueous dispersion and the water resistance of the resulting film. From such a point of view, ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are preferable as the neutralizing agent used for the salt of (c1).

  Among the components (c), preferred are 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid and their compounds from the viewpoint of the resin physical properties of the obtained film and the dispersion stability of the polyurethane resin composition aqueous dispersion. It is a salt, more preferably a neutralized salt of 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms.

The neutralizing agent used in (c) may be added at any time before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. From the viewpoint of the stability of the urethane resin and the stability of the aqueous dispersion, it is preferable to add it before the aqueous dispersion step or during the aqueous dispersion step. Further, the neutralizing agent volatilized at the time of solvent removal may be additionally added after solvent removal, and the neutralizing agent species to be additionally added can be freely selected from those described above.

The amount of (c) used is preferably such that the content of the hydrophilic group in (U) is 0.10 to 1.2 mmol / g, more preferably 0.10 to 1 based on the weight of (U). It is adjusted to be 1 mmol / g, more preferably 0.10 to 1.0 mmol / g.

In the case of (f2), examples of the polyurethane resin (U) having (f2) include polyurethane resins (U) obtained by using mono- or dialkanolamine as a reaction terminator in the synthesis reaction.
The mono- or dialkanolamines include monoethanolamine, diethanolamine and diisopropanolamine.

  The polyurethane resin (U) is not particularly limited as long as it has a functional group (f) having reactivity with the crosslinker (T), and it comprises, for example, an active hydrogen component (A) and a polyisocyanate (B). The component (A) is preferably a polyurethane resin having a polyol (a), a compound (c0) containing a hydrophilic group and two active hydrogen atoms, and a chain extender (d) as a constituent monomer.

Examples of the polyol (a) include polyols (a1) having a number average molecular weight (hereinafter abbreviated as Mn) of 300 or more, and low molecular polyols (a2) having a Mn of less than 300.
The Mn of the polyol in the present invention is measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard. However, Mn of the low molecular weight polyol is a calculated value from a chemical formula.

  Polyol (a) may use only 1 type among what is described below, and may use 2 or more types together.

  Examples of the polyol (a1) having a Mn of 300 or more include a polyether polyol (a11) and a polyester polyol (a12).

  As polyether polyol (a11), aliphatic polyether polyol and aromatic ring containing polyether polyol are mentioned.

  Examples of aliphatic polyether polyols include polyoxyalkylene polyols [polyethylene glycol (hereinafter abbreviated as PEG) and the like], polyoxypropylene polyols [polypropylene glycol and the like], polyoxyethylene / propylene polyol, polytetramethylene ether glycol and the like. It can be mentioned.

As an aliphatic polyether polyol, PTMG 1000 [poly (oxytetramethylene) glycol of Mn = 1,000, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG 2000 [poly (oxytetramethylene) glycol of Mn = 2,000, Mitsubishi Chemical Co., Ltd. product, PTMG 3000 [Mn (= 3,000 poly (oxytetramethylene) glycol), Mitsubishi Chemical Co., Ltd. product], PTGL 2000 (Mn = 2,000 modified poly (oxy tetramethylene) glycol, Hodogaya Chemical Manufactured by Kogyo Co., Ltd., PTGL 3000 [Mn = 3,000 modified poly (
And oxytetramethylene) glycol, Hodogaya Chemical Industry Co., Ltd., and Sannics diol GP-3000 (polypropylene ether triol having Mn = 3,000, Sanyo Chemical Industries, Ltd., etc.).

  Examples of aromatic polyether polyols include ethylene oxide of bisphenol A (hereinafter abbreviated as EO) adduct [EO 2 molar adduct of bisphenol A, EO 4 molar adduct of bisphenol A, 6 mol EO of bisphenol A, bisphenol A EO 8 molar adduct of bisphenol A, EO 10 molar adduct of bisphenol A, EO 20 molar adduct of bisphenol A, etc. and propylene oxide of bisphenol A (hereinafter abbreviated as PO) adduct [PO2 molar adduct of bisphenol A, bisphenol A Examples of the polyol having a bisphenol skeleton such as PO 3 mole adduct, PO 5 mole adduct of bisphenol A, etc., and EO or PO adduct of resorcin and the like.

  Mn of (a11) is preferably 300 or more, more preferably 300 to 10,000, and still more preferably 300 to 6,000, from the viewpoint of mechanical properties of the polyurethane resin (U).

  As polyester polyol (a12), condensation type polyester polyol, polylactone polyol, polycarbonate polyol, castor oil type polyol etc. are mentioned.

The condensation type polyester polyol is a polyester polyol of a low molecular weight (less than Mn 300) polyhydric alcohol and a polycarboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
As low molecular weight polyhydric alcohols, dihydric to octahydric or higher aliphatic polyhydric alcohols having an Mn of less than 300 and alkylene oxides of dihydric to octavalent or more phenols having an Mn of less than 300 (EO, PO, 1, 2 -, 1,3-, 2,3- or 1,4-butylene oxide and the like, hereinafter abbreviated as AO) low molar adduct can be used.
Among the low molecular weight polyhydric alcohols that can be used for condensation type polyester polyols, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, bisphenol A with low EO or PO molar ratio is preferable. Adducts and combinations of these.

  Aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.) as the C2-C10 polyvalent carboxylic acid or its ester-forming derivative that can be used for condensation type polyester polyol Alicyclic dicarboxylic acids (such as dimer acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid and phthalic acid), trivalent or higher polycarboxylic acids (such as trimellitic acid and pyromellitic acid), and the like Anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride and trimellitic anhydride etc.), acid halides thereof (such as adipic acid dichloride), low molecular weight alkyl esters thereof (such as dimethyl succinate and dimethyl phthalate) And combinations thereof.

  Specific examples of the condensation type polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyhexamethylene terephthalate 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-methyl pentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azet And polybutylene sebacate diol and poly Oh pliers Rutere terephthalate diol.

As commercial products of condensation type polyester polyols, San Estor 2610 [polyethylene adipate diol of Mn = 1,000, Sanyo Chemical Industries, Ltd. product], San Esther 4620 [polytetramethylene adipate diol of Mn = 2,000], Sun Esther 2620 [polyethylene adipate diol of Mn = 2,000, Sanyo Chemical Industries, Ltd.], Kuraray polyol P-2010 [poly-3-methyl-1,5-pentane adipate diol of Mn = 2,000], Kuraray polyol P-3010 [poly-3-methyl-1,5-pentane adipate diol of Mn = 3,000] and Kuraray polyol P-6010 [poly-3-methyl-1,5-pentane of Mn = 6,000] Adipate diol] and the like.

Polylactone polyols are polyadducts of lactones to the above low molecular weight polyhydric alcohols, and examples of lactones include lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone and ε-caprolactone), etc. Be
Specific examples of the polylactone polyol include, for example, polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

  As the polycarbonate polyol, the above-mentioned low molecular weight polyhydric alcohol, low molecular weight carbonate compound (for example, dialkyl carbonate having 1 to 6 carbon atoms of alkyl group, alkylene carbonate having alkylene group having 2 to 6 carbon atoms, and 6 to 9 carbon atoms And the like. Polycarbonate polyols and the like produced by condensation with dearylation reaction with an aryl group of The low molecular weight polyhydric alcohol and the alkylene carbonate may be used in combination of two or more.

  Specific examples of polycarbonate polyols include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, 3-methyl-5-pentane-carbonate diol, polytetramethylene carbonate diol and poly (tetramethylene / hexamethylene) carbonate diol (eg 1) Diol obtained by condensing 2,4-butanediol and 1,6-hexanediol in a dealcoholation reaction with dialkyl carbonate, and the like.

  Commercially available polycarbonate polyols include NIPPORAN 980R [Mn = 2,000 polyhexamethylene carbonate diol, manufactured by Nippon Polyurethane Industry Co., Ltd.], KURARAY polyol C-3090 [Mn = 3,000 poly (3-methyl-)]. 5-pentanediol / hexamethylene) carbonate diol], and T4672 [poly (tetramethylene / hexamethylene) carbonate diol of Mn = 2,000, Asahi Kasei Chemicals Co., Ltd. product] etc. are mentioned.

  Castor oil-based polyols include castor oil and modified castor oil modified with a polyol or AO. Modified castor oil can be produced by transesterification of castor oil with polyols and / or AO addition. Examples of castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, EO (4 to 30 mol) adducts of castor oil, and the like.

  Among the polyester polyols (a12), preferred are condensation type polyester polyols and polylactone polyols.

  Examples of low molecular weight polyols (a2) having an Mn of less than 300 include aliphatic dihydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1 , 8-octanediol, 1,4-cyclohexanedimethanol and their EO and / or PO adducts etc., aliphatic trihydric alcohols (glycerin, trimethylolpropane and these EO and / or PO adducts etc), and Examples thereof include aliphatic alcohols having 4 or more valences such as pentaerythritol, sorbitol and their EO and / or PO adducts. Among (a2), preferred is a divalent to trivalent aliphatic alcohol from the viewpoint of water resistance and thermal yellowing resistance, and an aliphatic trihydric alcohol can form a crosslinked structure in polyurethane resin particles, It is preferable at the point which can acquire the effect of the water resistance of a urethane membrane, and chemical-resistance improvement. As the aliphatic dihydric alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol are particularly preferable, and as the aliphatic trihydric alcohol, trimethylolpropane is particularly preferable.

As a compound (c0) containing a hydrophilic group and two active hydrogen atoms, a compound (c01) containing an anionic group and an active hydrogen atom and a compound (c02) containing a cationic group and an active hydrogen atom It can be mentioned.
As (c01), for example, a compound having a carboxyl group as an anionic group and having a carbon number of 2 to 10 [dialkylolalkanoic acid (for example, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid , 2,2-dimethylol heptanoic acid and 2,2-dimethylol octanoic acid), tartaric acid and amino acids (eg, glycine, alanine and valine etc.), sulfonic acid group as an anionic group, and having 2 to 2 carbon atoms 16 compounds [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester etc.], containing a sulfamic acid group as an anionic group, having 2 to 10 carbon atoms Compounds [N, N-bis (2-hydroxyethyl) sulfamic acid etc.] etc. and these compounds as neutralizing agents It includes the sum salt.

  As a compound (c02) containing a cationic group and an active hydrogen atom, for example, a compound having a tertiary amino group as a cationic group and having a hydroxyl group as an active hydrogen atom, a tertiary amino group-containing one to 20 carbon atoms Diol [N-alkyldialkanolamines (eg N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamines (eg N, N-dimethylethanolamine) And the like] and salts obtained by neutralizing the compound with a neutralizing agent.

  As a polyisocyanate (B), what is conventionally used for polyurethane resin manufacture can be used. As the polyisocyanate (B), an aromatic polyisocyanate (b1) having 6 to 20 carbon atoms having 2 to 3 or more isocyanate groups (excluding carbon in the isocyanate group, the same applies hereinafter), 2 to 2 carbon atoms 18 aliphatic polyisocyanates (b2), alicyclic polyisocyanates having 4 to 15 carbon atoms (b3), derivatives of aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms (b4) and (b1) to (b4) ( For example, isocyanurate compounds can be mentioned.

  Examples of the aromatic polyisocyanate (b1) having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4′- Or 2,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4 ', 4' '-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, crude MDI, etc. It can be mentioned.

  Examples of the aliphatic polyisocyanate (b2) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2 -Isocyanatoethyl-2, 6-diisocyanatohexanoate etc. are mentioned.

  Examples of the alicyclic polyisocyanate (b3) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) And bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and the like.

  As the aromatic aliphatic polyisocyanate (b4) having 8 to 15 carbon atoms, for example, m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethyl xylylene diisocyanate (TMXDI) Etc.

  Among the polyisocyanates (B), preferred are (b2) and (b3), more preferred (b3), particularly preferred IPDI and hydrogenated MDI, from the viewpoint of mechanical strength and weatherability of the resulting coating is there.

  As the chain extender (d), Mn or a low molecular weight polyol (a2) having a chemical formula weight of less than 300, water, diamines having 2 to 10 carbon atoms (eg ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine, Piperazine), C2-C10 polyalkylene polyamines (for example, diethylenetriamine, triethylenetetramine and tetraethylenepentamine), hydrazine or a derivative thereof (dibasic acid dihydrazide such as adipic acid dihydrazide, etc.), C2-C30 poly Epoxy compounds (eg, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and amino alcohols having 2 to 10 carbon atoms (eg, ethanolamine, diethanolamine, 2-amiles And the like.

  The polyurethane resin (U) in the present invention can use a reaction terminator if necessary. As the reaction terminator, monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.), monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, diamine) Mono- or dialkylamines such as butylamine and monooctylamine; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine etc. may be mentioned.

  The polyurethane resin (U) in the present invention can optionally contain additives such as an antioxidant, a coloring inhibitor, a weathering stabilizer, a plasticizer and a mold release agent. The amount of these additives used is preferably 10% by weight or less, more preferably 3% by weight or less, particularly preferably 1% by weight or less, based on the weight of (U).

The functional group (f) having reactivity with the crosslinking agent (T) is essentially contained in any of the constituent monomers described above, and reacts with the crosslinking agent (T) in a heating and drying process such as baking to obtain a crosslinked product. Form.
When the functional group (f) is a carboxyl group, the crosslinking agent (T) contains a crosslinking agent (T1) having two or more carbodiimide groups (t1) having reactivity with carboxyl groups in the molecule, an oxazoline group A crosslinking agent (T2) containing two or more of (t2) in the molecule, a crosslinking agent (T3) having two or more epoxy groups (t3) in the molecule, and the like are selected.
When the functional group (f) is a hydroxyl group, the crosslinking agent (T) contains a crosslinking agent (T3) having two or more epoxy groups (t3) having reactivity with the hydroxyl group in the molecule, and a silanol group (t4). The crosslinking agent (T4) etc. which have 2 or more in a molecule | numerator are selected.

As a heating condition which a crosslinking agent (T) and a functional group (f) may react, the temperature range of 50 degreeC-250 degreeC is preferable, and the range of the heating time of 0.5 minutes-120 minutes is preferable.

By appropriately adjusting the polyol (a), the polyisocyanate (B), the compound (c) containing a hydrophilic group and an active hydrogen atom, and the chain extender (d), the urethane group content of the polyurethane resin (U) can be desired. It can be in the range of
The urethane group content is preferably 0.5 to 3.0 mmol / g, more preferably 0.7 to 2.5 mmol / g, particularly preferably 0 from the viewpoint of mechanical physical properties, elongation at break and adhesion of the obtained film. 9 to 2.0 mmol / g.
The urethane group content is calculated from the N atom content quantified by the nitrogen analyzer and the ratio of the urethane group to the urea group quantified by 1 H-NMR and the allophanate group and the biuret group content.

  In the present invention, the urea group content in the polyurethane resin (U) is 1.5 mmol /% based on the weight of (U) from the viewpoints of film forming property and mechanical properties, elongation at break and adhesion of the obtained film. It is preferably at most g, more preferably at most 1.2 mmol / g, particularly preferably at most 1.0 mmol / g, particularly preferably at most 0.8 mmol / g.

In order to make the urea group content in the polyurethane resin (U) into a desired range, the amino group content, the water content and the isocyanate group content in the raw material of (U) may be appropriately adjusted.
The urea group content is calculated from the N atom content quantified by a nitrogen analyzer and the ratio of urethane group to urea group quantified by 1 H-NMR and the allophanate group and burette group content.

  In the present invention, the Mn of the polyurethane resin (U) is 5,000 or more, preferably 5,000 or more, more preferably 8,000 or more, from the viewpoints of mechanical properties, chemical resistance and the like of the obtained film. Most preferably, it is 10,000 or more.

  By appropriately adjusting the amount of the polyol (a), the polyisocyanate (B), the compound (c) containing a hydrophilic group and an active hydrogen atom, and the chain extender (d), the Mn of the polyurethane resin (U) can be desired. It can be in the range of

<Blocked polyisocyanate compound (J)>
The functional group (g) having reactivity with the crosslinking agent (T) in the present invention includes a carboxyl group and / or a carboxylate anion group (g1), and a hydroxyl group (g2).
The blocked polyisocyanate compound (J) is a blocked polyisocyanate compound in which a polyisocyanate compound (I) having a functional group (g) having reactivity with a crosslinking agent (T) is blocked with a blocking agent (E). Each component will be described below.

  As a polyisocyanate compound (I) having a functional group (g) having reactivity with a crosslinking agent (T), an isocyanate compound (I1) having a functional group (g) introduced to a part of the polyisocyanate (B), The isocyanate compound (I2) which introduce | transduced functional group (g) into a part of prepolymer (P1) of the isocyanate group terminal which consists of active hydrogen component (A) and polyisocyanate (B) is mentioned. (I1) and (I2) may be used alone or in combination.

Examples of the method for introducing the functional group (g) to part of the polyisocyanate (B) or (P1) include the following methods [1] and [2].
[1] A compound (X1) having a functional group (g) and having an active hydrogen group having reactivity with an isocyanate group is reacted with a part of the isocyanate group of polyisocyanate (B) or (P1) Just do it.
[2] The polyol (X2) having a functional group (g) is used in part of the polyol (a) which is a component of (P1). A part of polyol (a) is an amount which becomes content of the following functional group (g).

When the functional group (g) is a carboxyl group and / or a carboxylate anion group (g1), a hydroxy acid such as glycolic acid as (X1), or the carboxyl group and / or a carboxylate anion group as (X2) and compounds (c) containing g1) and two active hydrogen atoms.
When the functional group (g) is a hydroxyl group, examples of (X1) include mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine exemplified as the reaction terminator for the polyurethane resin (U). .

  (X1) and (X2) may be reacted after partially blocking the isocyanate group of the polyisocyanate compound (B) or (P1), or partially blocked the isocyanate group of (B) or (P1) You may make it react before doing. A part of isocyanate group is an amount which becomes content of the following functional group (g).

When a functional group (g) which itself has reactivity with an isocyanate group, such as a hydroxyl group, is introduced into a part of (B) or (P1), as (X1) Thus, in addition to the hydroxyl group, a compound having in the molecule an amino group having higher reactivity with the isocyanate group than the hydroxyl group may be used.
Specifically, as a method of introducing a hydroxyl group into a part of (B) or (P1), after blocking a part of the isocyanate group of (B) or (P1) with a blocking agent (e), The total amount of remaining isocyanate groups is reacted with the amino group of the mono- or dialkanolamines, or a part of the isocyanate group of (B) or (P1) is reacted with the amino group of the mono- or dialkanolamines After that, the entire amount of the remaining isocyanate group may be reacted with a blocking agent having an amino group or the like, which has higher reactivity than the hydroxyl group. A part of isocyanate group is an amount which becomes content of the following functional group (g).

  As reaction conditions at the time of making the isocyanate group of (B) or (P1) and the amino group of said mono or dialkanolamines, temperature of 20-40 degreeC is preferable, and reaction time of 5 minutes-1 hour is preferable. The reaction temperature and reaction time are preferable because the hydroxyl group of the mono- or dialkanolamines does not react with the isocyanate group of (B) or (P1).

  The reaction temperature for introducing the functional group (g) is preferably 20 to 120 ° C., more preferably 40 to 110 ° C. from the viewpoint of side reaction suppression. The reaction time is preferably 0.5 to 15 hours, more preferably 0.5 to 10 hours, from the viewpoint of side reaction suppression.

The average number of functional groups of the isocyanate group of (I) is preferably 2.0 or more, more preferably 2.5 or more from the viewpoint of adhesion.

  The isocyanate group content of the polyisocyanate compound (I) is calculated as weight% of isocyanate group (molecular weight 42) with respect to the weight of (I). The isocyanate group content of (I) is preferably 2.0 to 30.0% by weight from the viewpoint of adhesion.

  The content of the functional group (g) in the polyisocyanate compound (I) is 0 based on the weight of (I) from the viewpoint of mechanical properties of the polyurethane resin composition, adhesion, and storage stability of the aqueous dispersion. 15 to 2.5 mmol / g is preferable, more preferably 0.18 to 2.2 mmol / g, and more preferably 0.20 to 2.0 mmol / g.

  As the isocyanate blocking agent (E), lactams having 2 to 6 carbon atoms (eg, ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.), oximes having 1 to 15 carbon atoms [eg, acetoxime, methyl ethyl ketoxime (MEK) Oxime), methyl isobutyl ketoxime (MIBK oxime), cyclohexanone oxime, etc.], secondary amines having 2 to 15 carbon atoms [eg aliphatic amines (dimethylamine, diisopyramine, di-n-propylamine, diisobutylamine etc.), Alicyclic amines having 4 to 15 carbon atoms (methylhexylamine, dicyclohexylamine etc.), aromatic amines (aniline, diphenylamine etc.)], phenols having 6 to 20 carbon atoms and alkylphenols [eg phenol, cresol, ethylphenol, -Propylphenol, isopropylphenol, n-butylphenol, octylphenol, nonylphenol, xylenol, diisopropylphenol, di-t-butylphenol etc.], 5-membered ring compound having imino group and nitrogen-carbon double bond as a structural unit of the ring [ For example, imidazole, 2-methylimidazole, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 1,2,4-triazole etc.], imine [eg ethyleneimine, polyethyleneimine etc.], active methylene containing compound [eg malone Acid dimethyl, diethyl malonate, diisopropyl malonate, acetylacetone, methyl acetoacetate, ethyl acetoacetate etc], as described in Patent Publication Nos. 2002-309217 and 2008-239890. Of blocking agents, as well as mixtures of two or more thereof. Among these, preferred are oximes having 1 to 15 carbon atoms, secondary amines having 2 to 15 carbon atoms, 5-membered cyclic compounds having an imino group as a structural unit of the ring and a nitrogen-carbon double bond, and activity It is a methylene-containing compound, more preferably methyl ethyl ketoxime, diisopropylamine, 3,5-dimethylpyrazole, diethyl malonate.

  The blocked polyisocyanate compound (J) in the present invention is obtained by reacting the isocyanate compound (I) with the blocking agent (E). The reaction temperature is preferably 20 to 120 ° C., more preferably 40 to 110 ° C. from the viewpoint of side reaction suppression. The reaction time is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours from the viewpoint of side reaction suppression.

  It is also possible to use known urethanization catalysts (such as tin octylate and bismuth octylate) to accelerate the urethanization reaction between the active hydrogen component (A) and the polyisocyanate (B) in the polyisocyanate compound (I2) The amount of reaction catalyst used is preferably 1% or less, more preferably 0.001 to 0.1%, based on the weight of the resulting blocked polyisocyanate compound (J).

  The blocked polyisocyanate compound (J) of the present invention can further contain a plasticizer and / or an organic solvent for the purpose of adjusting its viscosity.

  Examples of plasticizers include aromatic carboxylic acid esters [diethyl phthalate (DEP), dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), phthalic acid such as dilauryl phthalate, distearyl phthalate and diisononyl phthalate (DINP) Esters, etc.], aliphatic carboxylic acid esters [methylacetylricinolate, di-2-ethylhexyl adipate (DOA), di-2-ethylhexyl sebacate (DOS), adipic acid-propylene glycol polyester and 2,2,4-trimethyl ester There may be mentioned 1,3--1,3-pentanediol diisobutyrate etc.], phosphoric esters [such as triphenyl phosphate and tricresyl phosphate] and mixtures of two or more of these. Among these, from the viewpoint of compatibility with (A), aromatic carboxylic acid esters are preferred, and DOP and DINP are more preferred.

  Organic solvents include ketone solvents (eg acetone and methyl ethyl ketone), ester solvents (eg ethyl acetate, dibasic acid ester (DBE)), ether solvents (eg tetrahydrofuran), amide solvents (eg N, N-dimethyl) Formamide and N-methylpyrrolidone), alcohol solvents (for example, isopropyl alcohol), and aromatic hydrocarbon solvents (for example, toluene) may be contained.

  A dissociation catalyst (n) may be used to lower the dissociation temperature of the blocking agent of the blocked polyisocyanate compound (J) to accelerate low temperature curing. The dissociation catalyst (n) includes a metal catalyst (n1) and an amine catalyst (n2). The metal catalyst (n1) and the amine catalyst (n2) may be used alone or in combination of two or more.

  As the metal catalyst (n1), an organic metal compound (n11) having a bond of metal (M) and carbon, a metal complex (n12) having a coordinate bond with the metal (M), and the metal (M) 1 type, or 2 or more types selected from the group which consists of carboxylic acid salt of (n13) is mentioned.

  Organometallic compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dimaleate, dibutyltin dioxide, dioctyltin oxide and the like as the organic metal compound (n11) Organic titanium such as tetra-n-butyl acid and tetraisopropyl titanate, organic bismuth, organic lead, organic nickel and the like can be mentioned.

  Examples of the metal complex (n12) include salts of acetylacetonate of metal (M) and the like, and examples thereof include tin acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate, lead acetylacetonate, zirconium acetylacetonate, iron Examples include acetylacetonate, aluminum acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, cobalt acetylacetonate and the like.

  Examples of the metal salts of carboxylic acids (n13) include tin carboxylates (tin octylate, tin acetate, tin laurate, tin oleate, etc.), bismuth carboxylates (bismuth octylate, bismuth naphthenate, etc.), lead carboxylates Systems (lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenate, etc.), nickel carboxylates (nickel octylate, nickel naphthenate, etc.), titanium carboxylates (titanium terephthalate, etc.), etc. It can be mentioned.

  Among the above metal catalysts (n1), preferred is one or more metals in which the metal (M) is selected from the group consisting of Sn, Bi, Ti, Pb, Zr, Fe, Al, Zn, and Mn. Organic metal compounds (n111) which are (M1), metal complexes (n121) having a coordinate bond with the metal (M1), and carboxylates (n131) of the metal (M) are more preferable. Dibutyltin dilaurate, tin octylate, bismuth octylate, bismuth naphthenate, tin acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate.

  Examples of the amine catalyst (n2) include primary to tertiary amines (n21) and quaternary ammonium salts (n22). The amine catalyst may be used alone or in combination of two or more.

  As the primary to tertiary amines (n21), bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, N-methyl- (dimethylaminopropyl) aminoethanolamine, dimorpholinodiethylether, dimethylaminoethanol , Dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, dimethylethanolamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, dimethylcyclohexylamine, methyldicyclohexylamine, triethylenediamine, tris (3-dimethylaminopropyl) Amine, tris (3-dimethylaminopropyl) hexahydro-s-triazine, tris (dimethyla) Nomethyl) phenol, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, methylmorpholine, ethylmorpholine, dimethylaminoethylmorpholine, 1,8-diazabicyclo [5,4,0] -undecene -7, 1,8-Diazabicyclo [5,4,0] -undecen-7 weak acid salt (phenol salt, 2-ethylhexanoate, formate etc.), 1,5-diazabicyclo [4,3,0] -Nonene-5, 1,5-diazabicyclo [4,3,0] -nonene-5 weak acid salt (phenol salt, 2-ethylhexanoate, formate etc.), 1,2-dimethyltetrahydropyrimidine, 2- Weak acid salt of dimethyltetrahydropyrimidine (phenol salt, 2-ethylhexanoate, formate etc.), tetramethylguanidine Can be mentioned.

  Examples of quaternary ammonium salts (n22) include the following weak salts of quaternary ammonium (phenol salts, 2-ethylhexanoate, formate and the like). Examples of quaternary ammonium include tetramethyl ammonium, methyl triethyl ammonium, ethyl trimethyl ammonium, propyl trimethyl ammonium, butyl trimethyl ammonium, pentyl trimethyl ammonium, hexyl trimethyl ammonium, heptyl trimethyl ammonium, octyl trimethyl ammonium, nonyl trimethyl ammonium, decyl trimethyl ammonium, Undecyl trimethyl ammonium, dodecyl trimethyl ammonium, tridecyl trimethyl ammonium, tetradecyl trimethyl ammonium, heptadecyl trimethyl ammonium, hexadecyl trimethyl ammonium, heptadecyl trimethyl ammonium, octadecyl trimethyl ammonium, triethyl methyl ammonium , Tetraethylammonium, tetrapropylammonium, tetrabutylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methyl mole Holinium, 1-methylpiperidinium, (2-hydroxypropyl) trimethylammonium as trialkylhydroxypropylammonium, (2-hydroxypropyl) triethylammonium, (2-hydroxypropyl) tripropylammonium, (2-hydroxypropyl) And tributylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol and the like.

  Among the amine catalysts (n2), preferred are amine catalysts containing a strong base having an acid dissociation constant (pKa) of 11 or more, more preferably 1,8-diazabicyclo [5,4,0] -Undecen-7, 1,8-diazabicyclo [5,4,0] -undecen-7 weak acid salt (phenol salt, 2-ethylhexanoate, formate etc.), 1,5-diazabicyclo [4,3,3 0] -Nonene-5, 1,5-diazabicyclo [4,3,0] -nonene-5 weak acid salt (phenolic acid, 2-ethylhexanoate, formate etc.), tetramethyl ammonium weak acid salt (phenolic acid) Salts, 2-ethylhexanoate, formate etc., weak acid salts of methyltriethylammonium (phenolic salts, 2-ethylhexanoate, formate etc.), weak acid salts of tetraethylammonium (phenolic salts, - ethyl hexanoate, formate salt, etc.), a (2-hydroxypropyl) weak acid salt of trimethylammonium (phenol salt, 2-ethyl hexanoate, formate salt, etc.).

The functional group (g) reacts with the crosslinking agent (T) in a heating and drying process such as baking to form a crosslinked body.
When the functional group (g) is a carboxyl group, the crosslinking agent (T) contains a crosslinking agent (T1) having two or more carbodiimide groups (t1) having reactivity with carboxyl groups in the molecule, an oxazoline group A crosslinking agent (T2) containing two or more of (t2) in the molecule, a crosslinking agent (T3) having two or more epoxy groups (t3) in the molecule, and the like are selected.
When the functional group (g) is a hydroxyl group, the crosslinking agent (T) contains a crosslinking agent (T3) having two or more epoxy groups (t3) having reactivity with the hydroxyl group in the molecule, and a silanol group (t4). The crosslinking agent (T4) etc. which have 2 or more in a molecule | numerator are selected.

The volume average particle diameter (Dv) of the polyurethane resin composition aqueous dispersion is preferably 0.01 to 1 μm, and from the viewpoint of the dispersion stability of the polyurethane resin composition aqueous dispersion, more preferably 0.02 to 0. And more preferably 0.03 to 0.4 μm. A viscosity is appropriate as (Dv) is 0.01 micrometer or more, handling property is favorable, and dispersion stability is good as it is 1 micrometer or less. Volume average particle size (Dv) is measured by a light scattering particle size distribution analyzer

<Method of Producing Polyurethane Resin Composition Aqueous Dispersion>
As a method for producing a polyurethane resin composition aqueous dispersion, for example, a polyurethane comprising a polyol (a), a polyisocyanate (B), and a compound (c) containing a hydrophilic group and an active hydrogen atom as constituent monomers After mixing the prepolymer (P2), the blocked polyisocyanate compound (J), and the neutralizing agent in a predetermined weight ratio, an aqueous medium is added and subjected to a mixing / dispersion step to form an aqueous dispersion and then reactive with (P2) There is a method of reacting a chain extender (d) having the following, and if necessary, distilling off the organic solvent used in the course of production. The crosslinking agent (T) may be mixed at any time after mixing of (P2) and (J), during the water dispersion process, after the water dispersion process, or after distilling off the organic solvent, but From the viewpoint of stability, mixing is preferably performed after the water dispersion step, and in particular, mixing is preferably performed after evaporation of the organic solvent.

  The polyurethane resin composition aqueous dispersion in the present invention may optionally use a (P2) dispersant (h) from the viewpoint of the dispersibility of (P2) and the stability of the aqueous dispersion.

  The dispersing agent (h) includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and other emulsifying dispersants. (H) may be used alone or in combination of two or more.

  The content of (h) is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, still more preferably 0.1 to 5% by weight based on the weight of the polyurethane resin (U). .

  The polyurethane resin composition aqueous dispersion in the present invention is an organic solvent [ketone solvent (eg acetone and methyl ethyl ketone), ester solvent (eg ethyl acetate), ether solvent (eg tetrahydrofuran), amide solvent (eg N, N) -Dimethylformamide and N-methylpyrrolidone), alcohol solvents (e.g. isopropyl alcohol) and aromatic hydrocarbon solvents (e.g. toluene) etc. may be contained.

  In the present invention, the polyurethane prepolymer (P2) is reacted by heating the polyol (a), the polyisocyanate (B), and the compound (c) containing a hydrophilic group and an active hydrogen atom in a heatable facility. It is obtained by For example, the raw material of (P2) is charged into a container and uniformly stirred, and then heated without stirring with a heating dryer or heating furnace, simple pressure reactor (autoclave), Kolben, uniaxial or biaxial kneading Include a method of heating and reacting while stirring or kneading with a machine, a plastomill, a universal kneader or the like.

  As a device for mixing the polyurethane prepolymer (P2) and the block polyisocyanate compound (J), the device used for the synthesis of the prepolymer (P2) can be used as it is.

  The reaction temperature for producing the polyurethane prepolymer (P2) is preferably 60 to 120 ° C., more preferably 60 to 110 ° C., from the viewpoint of the content of allophanate group and biuret group of (P2). Preferably it is 60-100 degreeC. The time for producing (P2) can be appropriately selected according to the equipment used, but generally 1 minute to 100 hours is preferable, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 20 hours. If it is this range, (P2) which can fully exhibit the effect of the present invention is obtained.

  In order to control the urethanation reaction rate, known reaction catalysts (such as tin octylate and bismuth octylate) and reaction retarders (such as phosphoric acid) can be used. The addition amount of these catalysts or reaction retarders is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, particularly preferably 0.01 to 1% by weight based on the weight of (P2). %.

The content of the crosslinkable functional groups (t1) to (t4) of the crosslinking agent (T) in the polyurethane resin (U) is from the viewpoint of mechanical properties and adhesion of the polyurethane resin composition, and storage stability of the aqueous dispersion. From the viewpoint of the weight of the polyurethane resin (U), it is preferably 0.10 mmol / g to 1.0 mmol / g, more preferably 0.12 mmol / g to 0.80 mmol / g, still more preferably X 0.13 mmol / g to It is 0.70 mmol / g.

  The apparatus for dispersing the polyurethane prepolymer (P2) in water is not particularly limited, and it is preferable to use a rotary dispersing and mixing apparatus, an ultrasonic dispersing machine, or a kneader. An apparatus is further preferred.

  As a rotary type dispersive mixing apparatus, for example, a mixing apparatus having a general stirring blade such as Max Blend or a helical blade, TK homomixer (manufactured by Primix Co., Ltd.), Claire Mix (manufactured by Emtechnics Co., Ltd.), film mix [Primix Co., Ltd.], Ultratarlux [IKA Co., Ltd.], Ebara Milder [Ebarahara Co., Ltd.], Cavitron (Eurotech Co., Ltd.), Biomixer [Nippon Seiki Co., Ltd.], etc. Is illustrated.

  When the dispersion is carried out by the rotary dispersing and mixing apparatus, an additive selected from a pH adjuster, an antifoamer, a foam inhibitor, an antioxidant, a coloring inhibitor, a plasticizer, a mold release agent, etc., if necessary. Can be added one or more. In addition, if necessary, solvent removal, concentration, dilution, etc. may be performed after dispersion.

An apparatus for reacting a chain extender (d) after dispersing a mixture of a polyurethane prepolymer (P2) and a block polyisocyanate compound (J) is not particularly limited. The reaction is preferably carried out while mixing.

The crosslinking agent (T) in the present invention is a compound having two or more functional groups capable of reacting with the functional group (f) and the functional group (g) in the molecule, and the functional group (f) and the functional group (g Reactive functional groups, such as an epoxy group, a carbodiimide group, an oxazoline group, a silanol group, are selected by the combination of these, and 1 type (s) or 2 or more types of these can be used. Among these, a carbodiimide group (t1) or an oxazoline group (t2) is preferable from the viewpoint of the reactivity and the pot life as a crosslinking agent, and the stability of the polyurethane resin composition aqueous dispersion.

The method of mixing the crosslinking agent (T) with the aqueous dispersion of the polyurethane resin (U) is not particularly limited, and the device used for the synthesis of the polyurethane prepolymer (P2), or the dispersion of the preprepolymer (P2) in water You can use the device you used to

  The solid content concentration (content of components other than volatile components) of the polyurethane resin composition aqueous dispersion obtained by the production method of the present invention is preferably 20 to 65% by weight from the viewpoint of easy handling of the aqueous dispersion. More preferably, it is 25 to 55% by weight. The solid content concentration is approximately 1 g of aqueous dispersion lightly spread on a petri dish, precisely weighed, and then precisely weighed after heating for 45 minutes at 130 ° C. using a circulating constant temperature drier. It can be obtained by calculating the ratio (percentage) of the remaining weight after heating to the weight.

  The viscosity of the polyurethane resin composition aqueous dispersion obtained by the production method of the present invention is preferably 1 to 100,000 mPa · s, more preferably 5 to 5,000 mPa · s. The viscosity can be measured at a constant temperature of 25 ° C. using a BL viscometer.

  The pH of the polyurethane resin composition aqueous dispersion obtained by the production method of the present invention is preferably 2 to 12, more preferably 4 to 10. The pH can be measured at 25 ° C. with pH Meter M-12 (manufactured by Horiba, Ltd.).

  When the polyurethane resin composition aqueous dispersion (Q) is used for an inkjet ink, in addition to (Q), a pigment, a moisturizing / stabilizing aid, an aqueous dispersion resin or a water-soluble resin, a viscosity modifier, an antifoaming agent, preservative The composition may contain an agent, an antidegradant, a stabilizer, an antifreeze agent, water and the like.

  As the pigment, inorganic pigments having a water solubility of 1 or less (for example, white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments and metallic pigments) and organic pigments (for example, For example, natural organic pigment synthesis type organic pigment, nitroso pigment, nitro pigment, pigment dye type azo pigment, azo lake made from water soluble dye, azo lake made from poorly soluble dye, lake made from basic dye, lake made from acid dye, xanthan lake Anthraquinone lake, pigments from vat dyes, and phthalocyanine pigments). The content of the pigment is preferably 50% by weight or less, more preferably 30% by weight or less based on the weight of the inkjet ink (L).

The moisturizing stabilizing aid is not particularly limited, but a compound having a hydroxyl group and having a boiling point of 100 ° C. or more is preferable. For example, diglycerin, propylene glycol, ethylene glycol, 1,3-propanediol, triethylene glycol monobutyl ether can be mentioned.

  Examples of the aqueous dispersion resin or the water-soluble resin include, for example, an aqueous dispersible or water-soluble polyurethane resin other than the polyurethane resin in the present invention, a polyacrylic resin, and a polyester resin.

Viscosity modifiers include thickeners such as inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose-based viscosity modifiers (such as methyl cellulose having a molecular weight of 20,000 or more, carboxymethyl cellulose and hydroxymethyl cellulose), proteins Viscosity modifiers (casein, sodium caseinate, ammonium caseinate, etc.), acrylics (sodium polyacrylate with an Mn of 20,000 or more, ammonium polyacrylates, etc.) and vinyl-based viscosity modifiers (Mn: 20,000 or more) Polyvinyl alcohol etc. are mentioned.
Examples of the antifoaming agent include long chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), silicone oils (such as polymethyl siloxane and polyether-modified silicone).

Examples of preservatives include organic nitrogen sulfur compound based preservatives and organic sulfur halide based preservatives.
Examples of antidegradants and stabilizers (such as UV absorbers and antioxidants) include hindered phenols, hindered amines, hydrazines, phosphorus, benzophenones and benzotriazole antidegradants and stabilizers. .
Examples of antifreeze agents include ethylene glycol and propylene glycol.
The content of the viscosity modifier, the antifoaming agent, the preservative, the antidegradant, the stabilizer and the antifreeze agent is preferably 5% by weight or less, more preferably 3% by weight based on the weight of the inkjet ink (L). % Or less.

  EXAMPLES The present invention will be further described by way of examples, but the present invention is not limited thereto. In the following, parts represent parts by weight.

<Production Example of Blocked Polyisocyanate Compound (J)>
<Production Example 1>
In a simple pressure reaction vessel equipped with a stirrer and thermometer, 44.9 parts of isocyanurate of hexamethylene diisocyanate ("Duranate TPA-100" manufactured by Asahi Kasei Corp.) and 1.8 parts of glycolic acid as compound (X), solvent Then, 30 parts of acetone was charged as it was, reacted at 80 ° C. for 5 hours, and then cooled to obtain a polyisocyanate compound (I1-1). Thereafter, 23.3 parts of 3,5-dimethylpyrazole is charged as an isocyanate blocking agent (E), and the blocking reaction is carried out at 70 ° C. for 2 hours, and a block polypolyisocyanate compound having a carboxyl group as a functional group (g) J-1) was obtained.

<Production Example 2>
In a simple pressure reaction vessel equipped with a stirrer and a thermometer, 41.5 parts of polyether polyol ("Sannicks PP-1000" manufactured by Sanyo Chemical Industries, Ltd .; molecular weight = 1000) and polyether polyol (manufactured by Sanyo Chemical Industries, Ltd.) "Sannicks TP-400"; molecular weight = 1000) Prepare 6.5 parts of a compound (X), 2.4 parts of 2,2-dimethylol propionic acid, 15.5 parts of tolylene diisocyanate and 30 parts of acetone as a solvent After reacting for 5 hours at 80 ° C. in a dry nitrogen atmosphere, the reaction product was cooled to obtain a polyisocyanate compound (I2-1). Thereafter, 4.1 parts of methyl ethyl ketone oxime as an isocyanate blocking agent (E) is charged at 40 ° C., blocking reaction is carried out at 70 ° C. for 2 hours, and a block polyisocyanate compound having a carboxyl group as a functional group (g) -2) was obtained.

<Production Example 3>
In a simple pressure reaction vessel equipped with a stirrer and thermometer, 36.0 parts of a buret of hexamethylene diisocyanate ("Duranate 24A-100" manufactured by Asahi Kasei Corp.) at 40 ° C, 30 parts of acetone as a reaction solvent, compound (X) Then, 4.3 parts of diethanolamine was charged, and reacted at 40 ° C. for 5 minutes to obtain a polyisocyanate compound (I1-2). Thereafter, 29.7 parts of diethyl malonate is charged as an isocyanate blocking agent (E), and blocking reaction is carried out at 70 ° C. for 2 hours to obtain a polyisocyanate compound (J-3) having a hydroxyl group as a functional group (g) Obtained.

<Comparative Production Example 1>
In a simple pressure reaction vessel equipped with a stirrer and a thermometer, 45.1 parts of isocyanurate of hexamethylene diisocyanate ("Duranate TPA-100" manufactured by Asahi Kasei Corp.) and 30 parts of acetone as a reaction solvent are charged. After being reacted for 5 hours, it was cooled to obtain a polyisocyanate compound (I1′-1). Thereafter, 24.9 parts of 3,5-dimethylpyrazole as an isocyanate blocking agent (E) is charged, and a blocking reaction is carried out at 70 ° C. for 2 hours, and a block polypolyisocyanate having no functional group (g) in the compound The compound (J'-1) was obtained.

Example 1
184.6 parts of polycarbonate diol ("Duranol G 4672" manufactured by Asahi Kasei Chemicals Corporation; Mn = 2,000) as a polyol (a1) and 1 as a polyol (a2) in a simple pressure reaction apparatus equipped with a stirrer and a heating device And 4-butanediol 4.5 parts, 26.1 parts of 2,2-dimethylol propionic acid as a compound (c) containing a hydrophilic group and an active hydrogen atom, 134.8 parts of hydrogenated MDI as a polyisocyanate (B) An acetone solution of polyurethane prepolymer (P2-1) was prepared by charging 150 parts of acetone as a reaction solvent and stirring at 85 ° C. for 12 hours to carry out a urethanization reaction.
Next, 100 parts of the block polyisocyanate compound (J-1), 13.8 parts of triethylamine as a neutralizing agent, and 69.6 parts of acetone as a diluting solvent are added to 500 parts of the polyurethane prepolymer (P2-1) thus obtained to make it uniform After that, 482 parts of water was added while stirring at 200 rpm, and the mixture of (P2-1) and (J-1) was dispersed in the aqueous medium.
To the obtained dispersion, 27.1 parts of a 10% by weight aqueous solution of ethylenediamine as a chain extender (d) is added, and after distilling off acetone at 65 ° C. for 8 hours under reduced pressure, water dispersion as a crosslinking agent (T) Water and added after homogenization by adding 49.2 parts of water-soluble multifunctional polycarbodiimide compound ("Carbodilite E05" manufactured by Nisshinbo Chemical Co., Ltd., active ingredient 40 wt%, carbodiimide equivalent 310) (T1-1) The fraction concentration was adjusted to 35.0% by weight to obtain a polyurethane resin composition aqueous dispersion (Q-1).

Example 2
As a crosslinking agent (T), a water-dispersible polyfunctional oxazoline group-containing compound (“Epocross K-2010E” manufactured by Nippon Shokubai Co., Ltd., 40 wt% of active ingredient, oxazoline equivalent 555) (T2-1) 88.1 A polyurethane resin composition aqueous dispersion (Q-2) was obtained in the same manner as in Example 1 except for the addition.

Example 3
Polyether polyol ("PTMG-2000" manufactured by Mitsubishi Chemical Corp .; Mn = 2,000) 220.2 parts, polyol (a2) as a polyol (a1) in a simple pressure reaction apparatus equipped with a stirrer and a heating device And 7.0 parts of 1,4-butanediol, 16.7 parts of 2,2-dimethylol propionic acid as a compound (c) containing a hydrophilic group and an active hydrogen atom, and 106.1 parts of IPDI as a polyisocyanate (B) As a reaction solvent, 150 parts of acetone was charged, and the mixture was stirred at 85 ° C. for 12 hours to carry out a urethanization reaction to produce an acetone solution of a polyurethane prepolymer (P2-2).
Next, 100 parts of block polyisocyanate compound (J-2), 8.8 parts of triethylamine as a neutralizing agent, and 74.5 parts of acetone as a diluting solvent are added to 500 parts of the obtained polyurethane prepolymer (P2-2) to make uniform After that, 482 parts of water was added while stirring at 200 rpm, and the mixture of (P2-2) and (J-2) was dispersed in the aqueous medium.
To the obtained dispersion, 24.8 parts of a 10% by weight aqueous solution of ethylenediamine as a chain extender (d) is added, and acetone is distilled off at 65 ° C. under reduced pressure for 8 hours, and then (T1) as a crosslinking agent (T) -1) 49.2 parts were added and homogenized, then water was added to adjust the solid content concentration to 35.0% by weight, to obtain a polyurethane resin composition aqueous dispersion (Q-3).

Example 4
(P2-2) 500 parts, (J-3) 100 parts, 8.8 parts of triethylamine as a neutralizing agent, and 74.5 parts of acetone as a diluting solvent are added and homogenized, and then 482 parts of water are stirred at 200 rpm. While the mixture of (P2-2) and (J-3) was dispersed in the aqueous medium.
As a chain extender (d), 86.8 parts of a 10% by weight aqueous solution of diethanolamine was added to the obtained dispersion, and acetone was distilled off under reduced pressure at 65 ° C. for 8 hours. Thereafter, a water-insoluble polyfunctional epoxy compound (Nagase ChemiX Co., Ltd. product "Denacol EX-212", active ingredient 100%, epoxy equivalent 138) (T3-1), 13.0 parts as a crosslinking agent (T) The solution was added while stirring at 5000 rpm using a biomixer, and water was further added to adjust the solid content concentration to 35.0% to obtain a polyurethane resin composition aqueous dispersion (Q-4).

Example 5
(P2-1) 500 parts, (J-3) 100 parts, 13.8 parts of triethylamine as a neutralizer, 69.6 parts of acetone as a dilution solvent are added and homogenized, then 482 parts of water are stirred at 200 rpm. While the mixture of (P2-1) and (J-3) was dispersed in the aqueous medium.
94.7 parts of 10% by weight aqueous diethanolamine solution was added as a chain extender (d) to the obtained dispersion, and acetone was distilled off at 65 ° C. for 8 hours under reduced pressure. Thereafter, as a crosslinking agent (T), 3-glycidoxypropylmethyldiethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd., 100% active ingredient, epoxy equivalent 236, silanol equivalent 79) (T4-1) 15.0 parts were added while stirring at 5000 rpm with a biomixer, and water was further added to adjust the solid content concentration to 35.0%, to obtain a polyurethane resin composition aqueous dispersion (Q-5).

Comparative Example 1
A polyurethane resin composition aqueous dispersion having a solid content concentration of 35.0% is prepared in the same manner as in Example 1 except that the crosslinking agent (T) is not used, and the crosslinking agent (T) is formed in (Q) The polyurethane resin composition aqueous dispersion (Q'-1) which does not contain is obtained.

Comparative Example 2
(P2-1) 13.8 parts of triethylamine as a neutralizer and 74.5 parts of acetone as a diluting solvent were added to 500 parts of (P2-1) and homogenized, and then 482 parts of water was added while stirring at 200 rpm, and (P2-1) was added It was dispersed in an aqueous medium.
As a chain extender (d), 27.1 parts of a 10% by weight aqueous solution of ethylene diamine was added to the obtained dispersion, and acetone was distilled off at 65 ° C. for 8 hours under reduced pressure. Thereafter, 49.2 parts of (T1-1) as a crosslinking agent (T) is added and homogenized, water is further added to adjust the solid content concentration to 35.0%, and a blocked polyisocyanate compound in (Q) A polyurethane resin composition aqueous dispersion (Q′-2) not containing (J) was obtained.

Comparative Example 3
(P2-1) 500 parts, (J'-1) 100 parts, 13.8 parts of triethylamine as a neutralizing agent, 69.6 parts of acetone as a dilution solvent are added and homogenized, and then 482 parts of water are stirred at 200 rpm The mixture of (P2-1) and (J'-1) was dispersed in an aqueous medium while adding.
As a chain extender (d), 27.1 parts of a 10% by weight aqueous solution of ethylenediamine was added to the obtained dispersion, and acetone was distilled off under reduced pressure at 65 ° C. for 8 hours. Thereafter, 15.0 parts of (T1-1) as a crosslinking agent (T) is added and homogenized, water is further added to adjust the solid content concentration to 35.0%, polyurethane resin composition aqueous dispersion (Q Got '-3).

Comparative Example 4
In the simple pressure reaction apparatus equipped with a stirrer and heating device, 193.6 parts of polycarbonate diol ("Duranol G 4672" manufactured by Asahi Kasei Chemicals Co., Ltd .; Mn = 2,000) as polyol (a1), 1 as polyol (a2) 21.6 parts of 2,4-butanediol, 134.8 parts of hydrogenated MDI as polyisocyanate (B), and 150 parts of acetone as a reaction solvent are charged, and the mixture is stirred at 85 ° C. for 12 hours to carry out a urethanization reaction (polyurethane prepolymer An acetone solution of P2′-1) was prepared.
500 parts of (P2′-1) obtained, 100 parts of (J-1), 35 parts of polyoxyalkylene alkyl ether as an emulsifier (“Naroacty CL 120” manufactured by Sanyo Chemical Industries, Ltd.), triethylamine 13.8 as a neutralizing agent After 69.6 parts of acetone as a dilution solvent was added and homogenized, 482 parts of water was added while stirring at 200 rpm, and a mixture of (P2′-1) and (J-1) was dispersed in an aqueous medium.
To the obtained dispersion, 27.1 parts of a 10% by weight aqueous solution of ethylenediamine as a chain extender (d) was added, and acetone was distilled off under reduced pressure at 65 ° C. for 8 hours. Thereafter, 49.2 parts of (T1-1) as a crosslinking agent (T) is added and homogenized, water is further added to adjust the solid content concentration to 35.0%, polyurethane resin composition aqueous dispersion (Q ' -4) was obtained.

Next, a method of producing an aqueous ink for inkjet will be described.
23 parts of the polyurethane resin composition aqueous dispersion (Q-1) obtained in Example 1, 15 parts of a pigment [carbon black aqueous dispersion (manufactured by Tokai Carbon Co., Ltd. "Aqua-Black 162", solid content 20 wt%], Twenty parts of propylene glycol, 20 parts of glycerin and 22 parts of water were blended as a moisturizing stabilizing aid, and mixed for 10 minutes to prepare an aqueous ink for inkjet (L-1).
Also for (Q-2) to (Q-5) and (Q'-1) to (Q'-4), the pigment, the moisturizing stabilizer, and the water are blended in the same ratio, and the ink for ink jet (L-2) To (L-5) and (L'-1) to (L'-4) were obtained.

Various physical property values and evaluation results of the polyurethane resin aqueous dispersions (Q-1) to (Q-5) and (Q'-1) to (Q'-4) are shown in Table 1.
The evaluation results of (L-1) to (L-5) and (L'-1) to (L'-4) are shown in Table 1.

In addition, the measuring method and evaluation method of various physical-property values in this invention are as follows.

<Method of evaluating film physical properties (break strength, break elongation)>
10 parts of the polyurethane resin composition aqueous dispersion (Q) is poured into a 10 cm long × 20 cm wide × 1 cm deep polypropylene mold so that the film thickness after water drying becomes 200 μm and dried at room temperature for 12 hours The physical properties of the film obtained by drying by heating at 105 ° C. for 3 hours with a circulating dryer were measured, and the breaking strength and breaking elongation were measured.
In addition, the measurement of breaking strength and breaking elongation is as described in JIS K7311. It performed based on the tension test.

<Method for evaluating image adhesion>
5 cm × 20 cm of coated aqueous ink (L-1) to (L-5) and (L'-1) to (L'-3) for inkjet prepared were produced [Aurora coat "Nippon Paper Co., Ltd. product" ] So that the film thickness after drying might be 2 micrometers, and it dried at 140 degreeC for 10 minutes, and produced the coating film.
The coated film thus obtained was rubbed 100 times back and forth with a coated paper which had been subjected to a load of 200 g for 100 coats using a Gakushin type fastness tester [NR-100 (manufactured by Daiei Scientific Seiki Mfg. Co., Ltd.)]. The change of the optical density of the surface was measured with a reflection densitometer [RD-19 "manufactured by Greatag Macbeth"].
Change of optical density = (optical density of coated surface before friction)-(optical density of coated surface after friction)

The dried films of the polyurethane resin composition aqueous dispersions (Q-1) to (Q-5) of Examples 1 to 5 exhibit excellent breaking strength and breaking elongation, and aqueous inks (L-1) to (L-). 5) The change in optical density was also small in the excellent image adhesion test.
On the other hand, in Comparative Example 1 in which the crosslinking agent (T) was not included and Comparative Example 2 in which the blocked isocyanate compound (J) was not included, the breaking strength of the dried film was low, and the change in optical density in the image adhesion test was large. Moreover, in Comparative Example 3 in which the blocked polyisocyanate compound to be used does not have a functional group (g), the change in optical density in the image adhesion test is large, and in Comparative Example 4 in which the polyurethane resin does not have a functional group (f). The breaking strength and the breaking elongation of the dried film were low, and the change in the optical density in the image contact test was also large.

  The polyurethane resin composition aqueous dispersion of the present invention comprises an inkjet ink, an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing, a binder composition for non-woven fabrics, for reinforcing fibers) Bleeding agent composition, binder composition for antibacterial agent, raw material composition for artificial leather / synthetic leather etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition and antifouling coating composition etc.), aqueous paper It can be used suitably for a processing agent composition, an aqueous ink composition, etc.

Claims (4)

  Polyurethane resin (U) having at least one functional group (f) selected from carboxyl group, carboxylate anion group and hydroxyl group, carbodiimide group (t1), oxazoline group (t2), epoxy group (t3) and silanol group A polyurethane resin composition aqueous dispersion containing a crosslinking agent (T) having at least two functional groups selected from (t4) in a molecule, a blocked polyisocyanate compound (J) and an aqueous medium And a polyisocyanate compound (I) having a functional group (g) which is at least one group selected from a carboxyl group, a carboxylate anion group and a hydroxyl group, and an isocyanate blocking agent ( Polyurethane resin composition aqueous dispersion (Q) which is a reaction product with E).   5) The isocyanate blocking agent (E) has an oxime having 1 to 15 carbon atoms, a secondary amine having 2 to 15 carbon atoms, an active methylene compound, and an imino group as a constituent unit of the ring and a nitrogen-carbon double bond The polyurethane resin composition aqueous dispersion according to claim 1, which is at least one member selected from the group consisting of ring compounds.   The polyurethane resin composition aqueous dispersion according to claim 1 or 2 for an inkjet ink.   An inkjet ink (L) containing the polyurethane resin composition aqueous dispersion (Q) according to any one of claims 1 to 3, a pigment, and a moisturizing stabilization aid.