JP4154521B2 - Water-based polyurethane resin, binder for printing ink, and printing ink composition - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to an aqueous polyurethane resin, a binder for printing ink, and a printing ink composition. More specifically, it has excellent adhesion to plastics such as polypropylene, nylon and polyester, and paint, ink, glass scattering prevention film, synthetic leather, artificial leather, non-woven fabric, woven fabric, paper, wood, steel plate, Aqueous polyurethane resin that can be suitably used for coating agents such as rubber, leather, floor polish, glass fiber sizing agent, adhesives, and adhesives, binders for printing inks and printing ink compositions containing the aqueous polyurethane resins Related to things.
[0002]
[Prior art]
Conventionally, polymer organic solvent solutions were mainly used as coating agents and adhesives such as paints and inks, but in recent years, prevention of pollution such as air pollution, regulations in the Fire Service Act, working conditions In view of safety and hygiene, water-soluble polymers and polymer emulsions have been used. As the water-soluble polymer, in recent years, an aqueous polyurethane resin characterized by its flexibility has been developed. However, in order to make a polyurethane water-based, it is necessary to add a polar group or the like to the polyurethane resin (see, for example, Patent Document 1), and therefore, for plastics (particularly polyolefin having no polar group). There was a drawback that adhesion was insufficient. In addition, a polyurethane resin for printing ink using a long chain monoamine compound as a chain length terminator has been proposed by the present applicant (see Patent Document 2), and this is a polyurethane for dissolving in a solvent other than water. It relates to a resin and cannot be used as an aqueous polyurethane resin, and the problem to be solved is also different.
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 11-269243 [Patent Document 2]
JP-A-2001-233929 [0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above prior art, and has flexibility specific to an aqueous polyurethane resin, and has excellent adhesion to plastics such as polyolefin (polyethylene, polypropylene, etc.), nylon, and polyester. It is an object of the present invention to provide an aqueous polyurethane resin having the same.
[0005]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies to solve the above problems, and found that the above problems can be solved by using an aqueous polyurethane resin obtained by reacting a specific monoalcohol compound or monoamine compound. It was.
[0006]
That is, the present invention is an aliphatic hydrocarbon compound having 10 to 40 carbon atoms having any one of a hydroxyl group, a primary amino group or a secondary amino group, a high molecular weight polyol (excluding a carboxyl group-containing high molecular weight polyol compound). , A polyisocyanate compound , and a reaction product obtained by reacting an aliphatic carboxylic acid selected from dimethylolpropionic acid, dimethylolbutanoic acid, and 2,2-dimethylolpentanoic acid with a neutralizing agent, Further, the present invention relates to an aqueous dispersion of a polyurethane resin having a carboxylate group dispersed in water ; a printing ink binder using the aqueous dispersion ; and a printing ink composition containing the printing ink binder.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The aliphatic hydrocarbon compound having 10 to 40 carbon atoms having any one of a hydroxyl group, a primary amino group or a secondary amino group, which is a constituent component of the aqueous polyurethane resin of the present invention, includes a hydroxyl group, a primary amino group or There is no particular limitation as long as it has any one of secondary amino groups and has 10 to 40 carbon atoms, and known ones can be used. Specifically, examples of the aliphatic hydrocarbon compound having 10 to 40 carbon atoms having one hydroxyl group include decyl alcohol, isodecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, And monoalcohols such as isostearyl alcohol, oleyl alcohol, and behenyl alcohol. Examples of the aliphatic hydrocarbon compound having 10 to 40 carbon atoms having one primary amino group include primary monoamines such as decylamine, laurylamine, myristylamine, stearylamine, and oleylamine. Examples of the aliphatic hydrocarbon compound having 10 to 40 carbon atoms having one secondary amino group include secondary monoamines such as di2-ethylhexylamine and distearylamine. These aliphatic hydrocarbon compounds can be used alone or in combination of two or more. When these aliphatic hydrocarbon compounds have less than 10 carbon atoms, the adhesion to various plastic films is inferior, which is not preferable. When the number of carbon atoms exceeds 40, overprinting is required when used in printing ink. This is not preferable because a problem such as occurrence of repellency occurs in this part.
[0008]
High molecular weight polyols (excluding carboxyl group-containing high molecular weight polyol compounds) include polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran; ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol , Octanediol, 1,4-butynediol, dipropylene glycol and other known low molecular weight glycols or unsaturated glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether Monocarboxylic acid glycidyl esters such as tellurium and versatic acid glycidyl ester, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelin Polyester polyols obtained by dehydration condensation of acid, azelaic acid, sebacic acid, dibasic acid such as suberic acid or the like, and acid anhydrides and dimer acids corresponding thereto; obtained by ring-opening polymerization of cyclic ester compound Polyester polyols; other known polycarbonate polyols, polybutadiene glycols, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, and various known high molecular weight polyols generally used in the production of polyurethane resins. That.
[0009]
A typical example of the polyisocyanate compound is a diisocyanate compound. Specific examples of the diisocyanate compound include, for example, methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate. A chain aliphatic diisocyanate such as dimerisocyanate in which the carboxyl group of dimer acid is replaced with an isocyanate group; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-di ( Cycloaliphatic diisocyanates such as isocyanate methyl) cyclohexane and methylcyclohexane diisocyanate; 4,4′-diphenyldi Dialkyldiphenylmethane diisocyanate such as methylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane Aromatic diisocyanates such as diisocyanate, 4,4′-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate; And amino acid diisocyanates. These polyisocyanate compounds including these diisocyanate compounds are used alone or in admixture of two or more. Among these diisocyanate compounds, weather resistance can be improved by using chain aliphatic diisocyanate and cycloaliphatic diisocyanate.
[0010]
The use ratio of the aliphatic hydrocarbon compound and the high molecular weight polyol is preferably about 1/99 to 20/80 by weight. When the amount of the aliphatic hydrocarbon compound used is less than the lower limit of the numerical range, the effect of the invention of being excellent in adhesion to various plastic films is hardly exhibited, and the upper limit of the numerical range In the case where it exceeds 1, it becomes difficult to increase the molecular weight of the finally obtained aqueous polyurethane resin, and the film strength and blocking resistance tend to be lowered.
[0011]
In the present invention, a chain extender can be used as necessary. Specific examples of the chain extender include, for example, low molecular weight glycols shown in the high molecular weight polyol section; ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine. , Amines such as triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine; 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethyl Diamine having a hydroxyl group in the molecule such as propylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc .; replacing the carboxyl group of dimer acid with an amino group Dimer diamine, hydrazine, such as adipic acid dihydrazide, and the like. These chain extenders are used alone or in admixture of two or more. Among these chain extenders, a chain extender having an ionic functional group can be used to impart an ionic functional group to the polyurethane resin for the purpose of improving the dispersibility in water. The ionic functional group is not particularly limited, and examples thereof include a quaternary amino base and a carboxylate base. Specific examples include N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-isobutyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, ethoxylated coconut oil amine, N-allyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-butyldiisopropanolamine, dimethyldiethoxyhydrazine, propoxymethyldiethanolamine, N- (3-aminopropyl) -N-methylethanolamine, N, N'-bis (oxyethyl) propylenediamine, diethanolaminoacetate Alkoxylated chain aliphatic amines such as amide, diethanolaminopropionamide, N, N-bis (oxymethyl) semicarbazide; alkoxylated cyclic aliphatic amines such as N-cyclohexyldiisopropanolamine; N, N-diethoxyaniline, N, N-diethoxytoluidine, N, N-diethoxy-1-aminopyridine, N, N′-bis (2-hydroxyethyl) -N, N′-diethylhexahydro-p-phenylenediamine, N, N ′ Alkoxylated aromatic amines such as bis (oxyethyl) phenyl semicarbazide; alkoxylated heterocyclic amines such as N, N′-diethoxypiperazine, N-2-hydroxyethylpiperazine; N-methyl-N, N-bis (3 -Aminopropyl) amine, N- (3-aminopropyl) -N, N'- Such as methylethylenediamine, N, N′-bis (3-aminopropyl) -N, N′-dimethylethylenediamine, 2-methyl-2-[(N, N-dimethylamino) methyl] propane-1,3-diol, etc. Chain aliphatic amines; aromatic amines such as 2,6-diaminopyridine and p, p′-bis-aminomethyldibenzylmethylamine; N, N′-bis (3-aminopropyl) piperazine, N- (2 -Aminoethyl) heterocyclic amines such as piperazine. Note that the basic nitrogen possessed by the chain extender is chloride ion, sulfate ion, organic carboxylic acid before the chain extender is dispersed in water or after the chain extender is dispersed in water. Is quaternized with a quaternizing agent such as
[0012]
In the present invention, as a chain extender having a carboxyl group, a carboxylate, are selected for introduction into Erareru polyurethane, dimethylol propionic acid, dimethylol butanoic acid, and 2,2-dimethylol pentanoic acid An aliphatic carboxylic acid is used . In addition, the carboxyl group possessed by the chain extender is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; ammonia; trimethylamine, triethylamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine or N-ethyldiethanolamine. Neutralization with neutralizing agents such as tertiary amines such as N-alkyldiethanolamine, N, N-dimethylethanolamine and N, N-diethylethanolamine Is done. The chain extender may be used before the polymerization component is dispersed in water, or may be used after the polymerization component is dispersed in water.
[0013]
The blending amount of the chain extender is not particularly limited, but from the viewpoint of achieving both flexibility and toughness of a film formed from the obtained aqueous polyurethane resin, 0.1 to 20% by weight of the polymerization component, It is desirable to adjust so that it may become 1 to 15 weight% preferably.
[0014]
The blending amount in the case of using the chain extender having an ionic functional group is not particularly limited. For example, basic nitrogen in the polyurethane resin having basic nitrogen is based on 1 g of resin solid content of the polyurethane resin. It is preferable to adjust to about 3 × 10 ^{−5 to} 1.8 × 10 ⁻³ gram equivalent. The amount of the chain extender having a carboxyl group which is a chain extender having an ionic functional group is not particularly limited. For example, the carboxyl group in the polyurethane resin having such a carboxyl group is It is preferable to adjust so that it may become about 3 * 10 < ^-5 > -1.8 * 10 < ^-3 > gram equivalent with respect to 1g of resin solid content.
[0015]
The aqueous polyurethane resin of the present invention can be obtained by reacting these components by a known method. The main components of the obtained aqueous polyurethane resin are the active hydrogen group of the aliphatic hydrocarbon compound having any one of a hydroxyl group, a primary amino group or a secondary amino group and a high molecular weight polyol. When the hydroxyl group reacts with the isocyanate group of the polyisocyanate. For example, when the active hydrogen group of the aliphatic hydrocarbon compound is a hydroxyl group, the active hydrogen group of the aliphatic hydrocarbon compound is an amino group via a urethane bond. Are bonded via a urethane bond and a urea bond. The number average molecular weight of the obtained aqueous polyurethane resin is usually about 3,000 to 1,000,000. The aqueous polyurethane resin of the present invention can be obtained by reacting each of the above components, but it is not usually isolated as an aqueous polyurethane resin, but is used as it is as an aqueous solution as a binder for printing ink. Below, the manufacturing method of the binder for printing inks by each method is demonstrated.
[0016]
Specific examples of the method of dispersing the aqueous polyurethane resin having an ionic functional group obtained by the method of imparting an ionic functional group in water include, for example, any one of a hydroxyl group, a primary amino group, and a secondary amino group An aliphatic hydrocarbon compound having 10 to 40 carbon atoms, a high molecular weight polyol and a polyisocyanate compound, and an aliphatic carbon compound having 10 to 40 carbon atoms having any one of a hydroxyl group, a primary or a secondary amino group A prepolymer having an NCO group is produced by copolymerization under the condition that the NCO group of the polyisocyanate compound is excessive with respect to the active hydrogen group of the hydrogen compound and the high molecular weight polyol, and the prepolymer is dissolved in a suitable organic solvent. Then, a chain extender containing a chain extender having an ionic functional group is added to the solution and reacted, and then A method of removing quaternization or neutralization using a quaternizing agent or a neutralizing agent, further dispersing in water and then removing the organic solvent as necessary, either hydroxyl group, primary amino group or secondary amino group A chain extender containing an aliphatic hydrocarbon compound having 10 to 40 carbon atoms, a high molecular weight polyol, a polyisocyanate compound, and a chain extender having the ionic functional group in an appropriate organic solvent. , Quaternization or neutralization using the quaternizing agent or neutralizing agent, followed by dispersing in water and then removing the organic solvent as necessary, hydroxyl group, primary amino group or An aliphatic hydrocarbon compound having any one of secondary amino groups having 10 to 40 carbon atoms, a high molecular weight polyol, a polyisocyanate compound, and a chain extender having the ionic functional group, a hydroxyl group, An aliphatic hydrocarbon compound having 10 to 40 carbon atoms having any one of a secondary amino group and a secondary amino group, a high molecular weight polyol, and an active hydrogen group of the chain extender having the ionic functional group The polyisocyanate compound is reacted in an appropriate organic solvent under the condition that the NCO group of the polyisocyanate compound is excessive to produce a prepolymer having an NCO group at the end of the molecule, and 4 using the quaternizing agent or neutralizing agent. Examples of the method include after classifying or neutralizing, dispersing in water, then adding a chain extender and reacting, and then removing the organic solvent as necessary. The organic solvent is not particularly limited as long as it is usually used. Specific examples of such organic solvents include aromatic solvents such as benzene, toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; dimethyl Amide solvents such as formamide; Sulfoxide solvents such as dimethyl sulfoxide; Ether solvents such as dimethyl ether and diethyl ether; Alcohols such as isopropyl alcohol and ethanol; N-methylpyrrolidone and the like. These organic solvents are used alone or in admixture of two or more.
[0017]
The printing ink binder thus obtained is subjected to kneading and dispersion by adding pigments and the like, and if necessary, an aqueous polyurethane resin, aqueous polyamide resin, aqueous acrylic ester different from those obtained in the present invention. A printing ink composition can be easily obtained by appropriately adding an aqueous resin such as a copolymer copolymer salt, an aqueous styrene-maleic acid copolymer salt, and additives such as an antiblocking agent and a plasticizer. .
[0018]
【The invention's effect】
According to the present invention, it has flexibility specific to an aqueous polyurethane resin, and particularly has excellent adhesion to plastics such as polyolefin (polyethylene, polypropylene, etc.), nylon and polyester when used as a binder for printing ink. An aqueous polyurethane resin can be provided. The water-based polyurethane resin has excellent adhesion, so that it is a paint, glass scattering prevention film, synthetic leather, artificial leather, nonwoven fabric, woven fabric, paper, wood, steel plate, rubber, leather, floor polish, glass fiber sizing agent. It can use suitably for coating agents, adhesives, pressure-sensitive adhesives, and the like.
[0019]
【Example】
Next, although the water-based polyurethane resin of this invention is demonstrated in detail based on an Example, this invention is not limited only to this Example.
[0020]
Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 26.4 parts of dimethylol butanoic acid, polypropylene glycol (trade name: Adeka Polyether P-2000, Asahi Denka Kogyo Co., Ltd., number average molecular weight 2 , 000) 362.0 parts, stearyl alcohol 25.9 parts, and isophorone diisocyanate 111.6 parts were charged and reacted at 85 ° C for 5 hours to obtain 525.9 parts of an isocyanate group-containing urethane prepolymer. The urethane prepolymer was cooled to 70 ° C. The urethane prepolymer was added and dispersed with stirring in an aqueous solution consisting of 914.0 parts of water, 74.0 parts of isopropyl alcohol, 17.8 parts of triethylamine, and 15.7 parts of adipic acid dihydrazide. Reacted for hours. The polyurethane resin aqueous dispersion thus obtained had a resin solid content concentration of 35%, a viscosity of 700 mPa · s / 25 ° C., and a pH of 8.0.
[0021]
Example 2
In a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 26.4 parts of dimethylol butanoic acid, polypropylene glycol (trade name: Adeka Polyether P-2000, Asahi Denka Kogyo Co., Ltd., number average molecular weight 2 , 000) 362.0 parts, 17.7 parts of laurylamine and 111.6 parts of isophorone diisocyanate were added and reacted at 85 ° C. for 5 hours to obtain 517.7 parts of an urethane prepolymer containing isocyanate groups. The urethane prepolymer was cooled to 70 ° C. The urethane prepolymer was added and dispersed with stirring in an aqueous solution consisting of 898.8 parts of water, 74.0 parts of isopropyl alcohol, 17.8 parts of triethylamine, and 15.7 parts of adipic acid dihydrazide. Reacted for hours. The polyurethane resin aqueous dispersion thus obtained had a resin solid content concentration of 35%, a viscosity of 800 mPa · s / 25 ° C., and a pH of 8.0.
[0022]
Comparative Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 26.4 parts of dimethylol butanoic acid, polypropylene glycol (trade name: Adeka Polyether P-2000, Asahi Denka Kogyo Co., Ltd., number average molecular weight 2 , 000) 362.0 parts and isophorone diisocyanate 71.8 parts were charged and reacted at 85 ° C. for 5 hours to obtain 460.2 parts of a urethane polymer. The urethane polymer was added and dispersed with stirring in an aqueous solution consisting of 762.9 parts of water, 74.0 parts of isopropyl alcohol, and 17.8 parts of triethylamine, and kept at 50 ° C. for 3 hours. The polyurethane resin aqueous dispersion thus obtained had a resin solid content concentration of 35%, a viscosity of 800 mPa · s / 25 ° C., and a pH of 8.0.
[0023]
Comparative Example 2
In a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 26.4 parts of dimethylol butanoic acid, polypropylene glycol (trade name: Adeka Polyether P-2000, Asahi Denka Kogyo Co., Ltd., number average molecular weight 2 , 000) 362.0 parts, 1-hexanol 9.8 parts, and isophorone diisocyanate 111.6 parts were charged and reacted at 85 ° C. for 5 hours to obtain 509.8 parts of an isocyanate group-containing urethane prepolymer. The urethane prepolymer was cooled to 70 ° C. The urethane prepolymer was added and dispersed with stirring in an aqueous solution consisting of 884.1 parts of water, 74.0 parts of isopropyl alcohol, 17.8 parts of triethylamine, and 15.7 parts of adipic acid dihydrazide. Reacted for hours. The polyurethane resin aqueous dispersion thus obtained had a resin solid content concentration of 35%, a viscosity of 1000 mPa · s / 25 ° C., and a pH of 8.0.
[0024]
Each polyurethane resin aqueous dispersion obtained in Example 1 and Comparative Example 1 was evaluated for the following items. The results are shown in Table 1.
[0025]
Adhesiveness: Each polyurethane resin aqueous dispersion was applied to a treated surface of a polypropylene film (OPP), polyethylene terephthalate film (PET), and nylon film (NY) treated with corona using a bar coder (No. 4). After being processed, it was dried with a heat gun for 1 minute to obtain a polyurethane resin coating film. Next, an adhesive tape was applied to the coated surface, and the remaining state of the coating film when peeled off in a direction perpendicular to the coated surface was visually evaluated.
○: No peeling at all.
Δ: 50% or more remained.
X: Less than 50% remained.
[0026]
[Table 1]

Claims (5)

An aliphatic hydrocarbon compound having 10 to 40 carbon atoms having any one of a hydroxyl group, a primary amino group or a secondary amino group, a high molecular weight polyol (excluding a carboxyl group-containing high molecular weight polyol compound), a polyisocyanate compound , and The reaction product obtained by reacting an aliphatic carboxylic acid selected from dimethylolpropionic acid, dimethylolbutanoic acid, and 2,2-dimethylolpentanoic acid is neutralized with a neutralizing agent, and further dispersed in water. An aqueous dispersion of a polyurethane resin having a carboxylate group . The aqueous dispersion according to claim 1, wherein the high molecular weight polyol (excluding the carboxyl group-containing high molecular weight polyol compound) is a polyether polyol . The weight ratio of the aliphatic hydrocarbon compound having 10 to 40 carbon atoms having any one of a hydroxyl group, a primary amino group, and a secondary amino group and a high molecular weight polyol is 1/99 to 20/80. The aqueous dispersion according to claim 1. The binder for printing inks using the water dispersion liquid in any one of Claims 1-3. A printing ink composition comprising the printing ink binder according to claim 4.