JP2003119241A - Aqueous polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin having the flexibility which aqueous polyurethane resins inherently possess, and excellent adhesion and blocking resistance to plastics such as nylons and polyesters. SOLUTION: The aqueous polyurethane which is used can be obtained by reacting a high molecular weight polyol, a hydride of a petroleum resin having active hydrogens, and a polyisocyanate compound as the major components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous polyurethane resin. More specifically, it has excellent adhesion and blocking resistance to plastics such as nylon and polyester, and has paints, inks, glass shatterproof films, synthetic leather, artificial leather, non-woven fabrics, woven fabrics, paper, wood, The present invention relates to an aqueous polyurethane resin which can be suitably used for a steel sheet, rubber, leather, floor polish, glass fiber sizing agent, coating agent for an ink jet receiving layer, adhesive, pressure sensitive adhesive and the like.

[0002]

2. Description of the Related Art Conventionally, polymer organic solvent solutions have been mainly used as coating agents and adhesives for paints, inks, etc., but in recent years, prevention of pollution such as air pollution, and fire prevention law. In consideration of regulations, safety of working conditions and hygiene, water-soluble polymers and polymer emulsions have come to be used. As the water-soluble polymer, an aqueous polyurethane resin having characteristics of flexibility has been developed in recent years, but the conventional aqueous polyurethane resin has a drawback that adhesion and blocking resistance to plastic are insufficient. was there.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art and has the flexibility peculiar to an aqueous polyurethane resin and has excellent adhesion to plastics such as nylon and polyester. And an aqueous polyurethane resin having blocking resistance.

[0004]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies to solve the above problems. As a result, by introducing a hydride of a petroleum resin into an aqueous polyurethane resin skeleton, the above problems are solved. I found that I could do it. The present invention has been completed based on such findings.

That is, the present invention provides an aqueous polyurethane resin obtained by reacting a high molecular weight polyol, a hydride of a petroleum resin having active hydrogen and a polyisocyanate compound as main components; a binder for a printing ink using the aqueous polyurethane resin. A printing ink composition containing the binder for a printing ink.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The hydride of a petroleum resin having active hydrogen, which is a constituent of the aqueous polyurethane resin of the present invention, is a polymerizable monomer (C5 fraction such as isoprene and normal pentene contained in petroleum fraction, C9 fraction such as styrene, vinyltoluene, α-methylstyrene and indene, cyclopentadiene fraction such as cyclopentadiene and dicyclopentadiene, a mixture thereof, a purified product thereof, or a separately synthesized polymerizable monomer. Etc.) and an active hydrogen-containing compound (a functional group containing an active hydrogen such as an alcoholic hydroxyl group, a phenolic hydroxyl group, an amino group or a carboxyl group capable of reacting with an isocyanate group (hereinafter referred to as “active hydrogen group”). Which is a compound having in the molecule) and a petroleum resin having active hydrogen Is a compound obtained by hydrogenation.

As the above-mentioned polymerizable monomer, since it exhibits good adhesion to various films and is easily hydrogenated, cyclopentadiene and C9 are used as C5 fractions.
As the fraction, aromatic hydrocarbons and separately synthesized polymerizable monomers corresponding to these compounds can be preferably used.

Examples of the active hydrogen-containing compound include an alcohol compound having a polymerizable unsaturated bond such as allyl alcohol, a hydroxyl group-containing compound such as a phenolic compound, and a carboxylic acid having a polymerizable unsaturated bond such as maleic acid or an anhydride thereof. Examples thereof include acid compounds, amine compounds having a polymerizable unsaturated bond such as aniline and allylamine. Of these, the phenolic compound is the amount of phenolic hydroxyl groups that can be introduced into the petroleum resin having active hydrogen (hydroxyl value).
There is a tendency to be limited to some extent. Further, a petroleum resin having active hydrogen having an active hydrogen group provided by a carboxylic acid compound having a polymerizable unsaturated bond such as maleic acid or its anhydride tends to be colored when hydrogenated. On the other hand, when an active hydrogen group is added by an alcohol compound having a polymerizable unsaturated bond such as allyl alcohol, it is easy to control the amount of hydroxyl groups, and it is difficult to color when a petroleum resin having active hydrogen is hydrogenated. There are advantages.

The above-mentioned petroleum resin having active hydrogen is prepared by allowing the above-mentioned active hydrogen-containing compound to exist in the reaction system at the time of polymerizing the above-mentioned polymerizable monomer and carrying out various known polymerization methods such as cationic polymerization method or thermal polymerization method. Can be manufactured

As another method for producing a petroleum resin having active hydrogen, a polymerized product of the above-mentioned polymerizable monomer and a compound having a functional group such as ester and a polymerizable unsaturated group in the molecule is hydrolyzed. There is a method of disassembling. Specifically, a monomer such as vinyl acetate is present when the polymerizable monomer is polymerized, and a polymer having an ester group introduced is synthesized by various known polymerization methods such as a cationic polymerization method or a thermal polymerization method. May be saponified to convert the ester group into a hydroxyl group.

Among the above methods, the method of reacting an active hydrogen-containing compound when polymerizing the above-mentioned polymerizable monomer is preferable from the viewpoint of its simplicity.

As the petroleum resin having active hydrogen, it is also possible to use a resin having a higher reactivity by further modifying the active hydrogen group introduced into the resin as described above. For example, when the active hydrogen group introduced into the resin is a hydroxyl group or a phenolic hydroxyl group,
It can be used as an adduct obtained by adding an alkylene oxide or an epoxy compound to these functional groups, and can also be used as an amidation product with a hydroxyamine compound when the active hydrogen group is a carboxyl group.

The thus-obtained petroleum resin having active hydrogen has active hydrogen in its molecule, and therefore can react with a diisocyanate compound. When the polymerizable monomer is a C9 fraction, the resin is preferably phenol or the like as an active hydrogen-containing compound to be reacted therewith, and the polymerizable monomer is a cyclopentadiene-based fraction such as cyclopentadiene or dicyclopentadiene. When it is, allyl alcohol or the like is preferable as the active hydrogen-containing compound to be reacted therewith, but in particular, an alcohol-modified dicyclopentadiene system capable of increasing the average hydroxyl group content per molecule of the obtained active hydrogen-containing petroleum resin. The use of a resin is preferable because the obtained polyurethane resin can have a high molecular weight.

The amount of active hydrogen in the petroleum resin having active hydrogen is, for example, when the active hydrogen-containing group is a hydroxyl group, the hydroxyl value is about 70 to 250, preferably 100 to 250.
220 is preferable. If the hydroxyl value is less than 70,
The reactivity between the hydride of the petroleum resin having the active hydrogen and the diisocyanate compound is lowered, and the adhesiveness and blocking resistance of the resulting polyurethane resin tend to be lowered. On the other hand, when the hydroxyl value is greater than 250, the water resistance of the resulting polyurethane resin tends to deteriorate.

The hydride of a petroleum resin having active hydrogen used in the present invention is subjected to a hydrogenation reaction in the state where the above-mentioned petroleum resin having active hydrogen is melted or dissolved in a solvent under various known hydrogenation catalysts. It is what you do and get.

As the reaction conditions for the hydrogenation reaction, the hydrogenation pressure is about 1 to 30 MPa, preferably 3 to 25 MP.
a and the reaction temperature is about 50 to 350 ° C, preferably 100 to 320 ° C. When the hydrogenation pressure is less than 1 MPa or the reaction temperature is less than 50 ° C., the hydrogenation reaction tends to be difficult to proceed. Hydrogenation pressure is 3
If it exceeds 0 MPa, special equipment is required,
When the reaction temperature exceeds 350 ° C, the decomposition reaction of the resin tends to be remarkable. The reaction time for hydrogenation is usually about 10 minutes to 10 hours, preferably 20 minutes to
7 hours. If the reaction time is less than 10 minutes,
Since the hydrogenation reaction is difficult to proceed, it is necessary to use a large amount of catalyst. If the reaction time exceeds 10 hours, the productivity tends to be poor. In addition, the above-mentioned range does not exclude hydrogenation conditions outside the range, and for example, a hydrogenation reaction can be performed by using a catalyst that can react even at a hydrogenation pressure of less than 1 MPa. It can be performed.

As the hydrogenation catalyst, various metals such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium and rhenium or metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be used by supporting it on a carrier such as porous alumina having a large surface area, silica, silica alumina (diatomaceous earth), carbon or titania. The amount of the catalyst used is usually about 0.01 to 10% by weight based on the modified hydrocarbon resin as the raw material resin.

Regarding the hydrogenation reaction time and the amount of the catalyst used, the case of using the batch system as the reaction system has been described, but other reaction systems such as the flow system (fixed bed system, fluidized bed system). It is also possible to adopt.

As a solvent used in the hydrogenation reaction, a petroleum resin having an active hydrogen as a raw material resin or a hydride of a petroleum resin having an active hydrogen as a product, which is inert in the reaction, can be dissolved. Any solvent can be used without particular limitation. For example, tetrahydrofuran, dioxane, n-hexane, n-heptane, n-octane,
2-ethylhexane, cyclohexane, decalin, terpene, isopropyl alcohol, n-butanol, 2-
Methyl-2-propanol, cyclohexanol, n-
Hexanol, 2-ethylhexanol, non-aromatic hydrocarbon solvent (for example, trade name "Shellsol D
-40 "manufactured by Shell Japan Co., Ltd.), an isoparaffin hydrocarbon solvent (for example," Shellzol D-70 "manufactured by Shell Japan Co., Ltd.), and various other known mineral spirits, and the like, or one or two of them. The above can be used in combination. The amount of the solvent used is not particularly limited, but is usually 5% by weight or more, preferably 10 to 70% by weight, based on the modified hydrocarbon resin.

The hydride of petroleum resin having active hydrogen is
Usually, the hydrogenation rate is 5 to 100%, and the color tone is excellent as 3 or less based on Gardner color number (JIS K5400).

The number average molecular weight of the hydride of a petroleum resin having active hydrogen is not particularly limited, but in view of workability, it is usually preferably about 200 to 3000.

Further, a hydride of a petroleum resin having active hydrogen contains an active hydrogen group which reacts with an isocyanate group in the molecule and thus can be used as a constituent component of the polyurethane resin of the present invention. As the active hydrogen group, an amino group, a carboxyl group and the like are preferable in terms of reactivity with isocyanate, but a hydroxyl group is particularly preferable in terms of no odor or coloration and easy production.

As the high molecular weight polyol, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3 -Propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol,
Various known saturated or unsaturated low molecular weight glycols such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butynediol and dipropylene glycol, or n-butylglycidyl Ether, alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, and adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid Polyester polyols obtained by dehydration condensation of dibasic acid such as oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or acid anhydrides or dimer acids corresponding thereto; Ring-opening of cyclic ester compound Polyester polyols obtained by other methods; 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 for producing polyurethane resins. Can be given. Among these, water-soluble polyols are preferable because the water-based polyurethane resin has good dispersibility in water. The water-soluble polyol is not particularly limited, and known ones can be used. Specifically, for example,
Examples thereof include polyoxyethylene glycols and polyester polyols containing polyoxyethylene glycols as an alcohol component. The blending amount of the water-soluble polyol is not particularly limited and may be appropriately adjusted depending on the type of the water-soluble polyol to be used. When polyoxyethylene glycol is used, for example, the dispersion stability in water is Therefore, it is desirable to adjust the resin solid content of the obtained aqueous polyurethane resin to be 20% by weight or more, and from the viewpoint of water resistance, the resin solid content of the obtained aqueous polyurethane resin should be 80% by weight or less.

A typical example of the polyisocyanate compound is a diisocyanate compound. Specific examples of the diisocyanate compound include 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,
Cyclic aliphatic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;
Dialkyldiphenylmethane diisocyanates such as 4,4′-diphenyldimethylmethane diisocyanate,
Tetraalkyldiphenylmethane diisocyanate such as 4,4′-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4
′ -Diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-
Examples thereof include aromatic diisocyanates such as dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate; amino acid diisocyanates such as lysine diisocyanate. The polyisocyanate compounds including these diisocyanate compounds may be used alone or in admixture of two or more. Among these diisocyanate compounds, weather resistance can be improved by using a chain aliphatic diisocyanate and a cyclic aliphatic diisocyanate.

The use ratio of the hydride of the above-mentioned petroleum resin having active hydrogen and the high molecular weight polyol is 1/99 by weight.
It is preferably ˜70 / 30. When the hydride of the petroleum resin having active hydrogen is less than 1, the adhesion and blocking resistance which are the effects of the present invention do not sufficiently appear, and when it exceeds 70, the flexibility characteristic of the aqueous polyurethane resin tends to be impaired. is there. Further, the mixing ratio of the high molecular weight polyol, the hydride of the petroleum resin having active hydrogen and the polyisocyanate compound is from the viewpoint of the drying property and blocking resistance of the obtained aqueous polyurethane, the petroleum resin having the high molecular weight polyol and active hydrogen. The molar ratio of the active hydrogen group of the hydride to the NCO group of the polyisocyanate compound (hereinafter referred to as NCO group / active hydrogen group ratio) is 1.1 / 1 or more, preferably 1.3 / 1 or more. In order to prevent the film formed from the obtained aqueous polyurethane resin from becoming too hard, the NCO group / active hydrogen group ratio is 10/1 or less, preferably 8/1 or less. It is desirable to adjust so that

In the present invention, a chain extender can be used if necessary. Specific examples of the chain extender include, for example, the low molecular weight glycols shown in the section of the high molecular weight polyol; ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-. Amine such as diamine; 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. Diamines having a hydroxyl group in the molecule; dimer diamines obtained by replacing the carboxyl group of dimer acid with amino groups, hydrazine, adipic acid dihydrazide, etc. It is. These chain extenders may be used alone or in admixture of two or more. Among these chain extenders, it is preferable to use a chain extender having an ionic functional group in order to impart an ionic functional group to the polyurethane resin for the purpose of improving dispersibility in water. As the ionic functional group,
Although not particularly limited, examples thereof include a quaternary amino base and a carboxylate group. As a specific example, N-methyldiethanolamine, N-ethyldiethanolamine,
N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N
-Isobutyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, ethoxylated palm oil amine, N-allyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-butyldiamine Isopropanolamine,
Dimethyldiethoxyhydrazine, propoxymethyldiethanolamine, N- (3-aminopropyl) -N-methylethanolamine, N, N'-bis (oxyethyl) propylenediamine, diethanolaminoacetamide, diethanolaminopropionamide, N, N-
Alkoxylated chain aliphatic amines such as bis (oxymethyl) semicarbazide; alkoxylated cycloaliphatic amines such as N-cyclohexyldiisopropanolamine;
N, N-diethoxyaniline, N, N-diethoxytoluidine, N, N-diethoxy-1-aminopyridine,
N, N'-bis (2-hydroxyethyl) -N, N'-
Diethyl hexahydro-p-phenylenediamine, N,
Alkoxylated aromatic amines such as N'-bis (oxyethyl) phenylsemicarbazide; Alkoxylated heterocyclic amines such as N, N'-diethoxypiperazine, N-2-hydroxyethylpiperazine; N-methyl-N, N-bis (3-aminopropyl) amine, N- (3-aminopropyl) -N, N'-dimethylethylenediamine, N,
Chain aliphatic amines such as N'-bis (3-aminopropyl) -N, N'-dimethylethylenediamine and 2-methyl-2-[(N, N-dimethylamino) methyl] propane-1,3-diol 2,6-diaminopyridine,
aromatic amines such as p, p′-bis-aminomethyldibenzylmethylamine; heterocyclic amines such as N, N′-bis (3-aminopropyl) piperazine and N- (2-aminoethyl) piperazine. To be The basic nitrogen contained in the chain extender is a chloride ion, a sulfate ion, or an organic carboxylic acid before the chain extender is dispersed in water or after the chain extender is dispersed in water. It is quaternized by using a quaternizing agent such as anion.

The chain extender having a carboxyl group is
It is used when introducing a carboxylic acid group into an obtainable polyurethane, and specific examples thereof include glyceric acid, dioxymaleic acid, dioxyfumaric acid, tartaric acid,
Dimethylolpropionic acid, dimethylolbutanoic acid,
2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, 4,4-di (hydroxyphenyl) valeric acid,
Aliphatic carboxylic acids such as 4,4-di (hydroxyphenyl) butyric acid; and aromatic carboxylic acids such as 2,6-dioxybenzoic acid. The carboxyl group of the chain extender includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia; trimethylamine, triethylamine, triethanolamine,
Such as N-alkyldiethanolamine such as triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine, and N, N-dialkylethanolamine such as N, N-dimethylethanolamine and N, N-diethylethanolamine. It is neutralized with a neutralizing agent such as a tertiary amine. Also,
Such a chain extender may be used before dispersing the polymerization component in water, or may be used after dispersing the polymerization component in water.

The amount of the chain extender to be blended is not particularly limited, but from the viewpoint of achieving both flexibility and toughness of the film formed from the obtained aqueous polyurethane resin, 1 to 20% by weight of the polymerizing component is used. It is desirable to adjust the content to be preferably 3 to 10% by weight.

The chain extender having the ionic functional group is used.
If there is no particular limitation, the compounding amount is not particularly limited.
Basic Nitrogen in Polyurethane Resin Having Basic Nitrogen
Fluorine is added to the resin solid content of 1g of the polyurethane resin.
3 x 10^-5~ 1.8 x 10^-3It becomes about gram equivalent
It is preferable to adjust so that. Also, the ionic officer
A chain having a carboxyl group, which is a chain extender having a functional group
The amount of the extender compounded is not particularly limited.
Carbohydrate in Polyurethane Resin Having Carboxyl Group
The xyl group corresponds to 1 g of resin solid content of the polyurethane resin.
Then 3 × 10 ^-5~ 1.8 x 10^-3About gram equivalent
It is preferable to adjust so that

In the present invention, a chain length terminator may be used if necessary. Specific examples of the chain length terminator include:
Examples thereof include monoamines such as di-n-butylamine and diethanolamine; monohydric alcohols such as ethanol and isopropanol. These chain length terminators may be used alone or in admixture of two or more.

The amount of the chain length terminator blended is not particularly limited, but from the viewpoint of facilitating the control of the molecular weight of the obtained aqueous polyurethane resin, 0.1 to 5 of the above-mentioned polymerization component is used.
It is desirable to adjust the content to be 0.5% by weight, preferably 0.5 to 3% by weight.

The aqueous polyurethane resin of the present invention can be obtained by reacting these components by a known method. The main component of the obtained aqueous polyurethane resin is
The hydroxyl group of the high molecular weight polyol and the active hydrogen group of the hydride of the petroleum resin having active hydrogen react with the isocyanate group of the polyisocyanate, for example, when the active hydrogen group of the petroleum resin is an alcoholic hydroxyl group or a phenolic hydroxyl group. Via a urethane bond, via an urethane bond and a urea bond when the active hydrogen group of the petroleum resin is an amino group, and via a urethane bond and an amide bond when the active hydrogen group of the petroleum resin is a carboxyl group. It is a combination. The number average molecular weight of the obtained aqueous polyurethane resin is usually about 5,000 to 100,000. As a method for improving the dispersibility of water-based polyurethane in water, a method using a water-soluble polyol and a method for imparting an ionic functional group to the obtained water-based polyurethane resin are exemplified, but at least one of these methods is used. Is effectively adopted. The aqueous polyurethane resin of the present invention can be obtained by reacting the above-mentioned components, but it is usually not isolated as an aqueous polyurethane resin but used 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.

As a method for dispersing the aqueous polyurethane resin obtained by using the water-soluble polyol in water, for example, a high-molecular weight polyol containing a water-soluble polyol such as polyoxyethylene glycol, hydrogen of a petroleum resin having active hydrogen is used. Hydride, a polyisocyanate compound and, if necessary, a chain extender or chain terminating agent, a high molecular weight polyol containing a water-soluble polyol with respect to the NCO group of the polyisocyanate compound, a hydride of a petroleum resin having active hydrogen , A chain extender and a chain length terminating agent are copolymerized under conditions where the active hydrogen groups are excessive, and then added to a suitable organic solvent, and the resulting polyurethane resin solution is dispersed in water, and if necessary, an organic solvent is added. Removal method, high molecular weight polyol containing water-soluble polyol such as polyoxyethylene glycol , A polyisocyanate compound having a hydride of a petroleum resin having active hydrogen and a polyisocyanate compound with respect to a total of active hydrogen groups of a high molecular weight polyol containing a water-soluble polyol and a hydride of a petroleum resin having active hydrogen Copolymerization is carried out under conditions in which the NCO group becomes excessive to form a prepolymer having an NCO group at the end of the molecular chain, and a solution prepared by adding such a prepolymer to an appropriate organic solvent is dispersed in water, A method in which a chain extender and, if necessary, a chain length terminator are added to the mixture to allow the reaction to proceed, and then the organic solvent is removed can be mentioned. The organic solvent is not particularly limited, and may be a commonly used one.
Specific examples of such an organic solvent include, for example, benzene,
Aromatic solvents such as toluene and xylene; ethyl acetate,
Ester solvents such as butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone; amide solvents such as dimethylformamide; 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 can be mentioned. These organic solvents may be used alone or in admixture of two or more.

Specific examples of the method of dispersing the ionic functional group-containing aqueous polyurethane resin obtained by the method of imparting an ionic functional group in water include, for example, high molecular weight polyol and hydrogen of petroleum resin having active hydrogen. And a polyisocyanate compound are copolymerized at the terminal of the molecular chain by copolymerizing the polyisocyanate compound and the NCO group of the polyisocyanate compound in excess of the active hydrogen group of the hydride of the petroleum resin having a high molecular weight polyol and active hydrogen. A chain extender containing a chain extender having the above ionic functional group in a solution of a prepolymer having an NCO group, prepared as a solution in a suitable organic solvent, and a chain terminator if necessary Is added and reacted, and then quaternized or neutralized using the above-mentioned quaternizing agent or neutralizing agent, and further dispersed in water. After that, a method of removing an organic solvent as required, a high molecular weight polyol, a hydride of a petroleum resin having active hydrogen, a polyisocyanate compound, a chain extender containing the chain extender having the ionic functional group, and if necessary Chain reaction with a chain terminating agent in a suitable organic solvent at once, and then quaternization or neutralization is carried out using the quaternizing agent or neutralizing agent described above, followed by dispersing in water, if necessary. Method for removing organic solvent, high molecular weight polyol, hydride of petroleum resin having active hydrogen, polyisocyanate compound and chain extender having ionic functional group, high molecular weight polyol, hydride of petroleum resin having active hydrogen And suitable under the condition that the NCO group of the polyisocyanate compound is excessive with respect to the active hydrogen group of the chain extender having the ionic functional group. A prepolymer having an NCO group at the end of the molecule is formed by reacting in an organic solvent, quaternization or neutralization is performed using the quaternizing agent or neutralizing agent, and then dispersed in water. Examples thereof include a method in which a chain extender and, if necessary, a chain length terminator are added and reacted, and then the organic solvent is removed as necessary.

Among these, since an aqueous polyurethane resin excellent in dispersion stability and water resistance can be obtained,
It is preferable to use an aqueous polyurethane resin having an ionic functional group.

The printing ink binder thus obtained is kneaded and dispersed by adding a pigment or the like,
If necessary, an aqueous polyurethane resin different from that obtained in the present invention, an aqueous polyamide resin, an aqueous acrylic acid ester-based copolymer salt, an aqueous resin such as a salt of an aqueous styrene-maleic acid-based copolymer, an antiblocking agent. A printing ink composition can be easily obtained by appropriately adding additives such as or plasticizer.

The reason why the aqueous polyurethane resin obtained by the present invention has excellent adhesion and blocking resistance to plastics such as nylon and polyester is not clear, but it is a hydride of petroleum resin which is tough and excellent in heat resistance. It is considered that the skeleton of is based on the fact that it is contained in such an aqueous polyurethane resin.

[0038]

EFFECTS OF THE INVENTION According to the present invention, it has flexibility peculiar to an aqueous polyurethane resin, and particularly when it is used as a binder for printing ink, it has excellent adhesion and blocking resistance to plastics such as nylon and polyester. It is possible to provide an aqueous polyurethane resin having In addition,
Since the water-based polyurethane resin has excellent adhesion and blocking resistance, it is used as a paint, a glass shatterproof film, synthetic leather,
It can be suitably used for artificial leather, non-woven fabric, woven fabric, paper, wood, steel plate, rubber, leather, floor polish, glass fiber sizing agent, coating agent for ink jet receiving layer, adhesive, pressure sensitive adhesive and the like.

[0039]

EXAMPLES Next, the aqueous polyurethane resin of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1 In a reaction vessel equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introducing tube, 59.4 parts of dimethylolbutanoic acid and polypropylene glycol 312.8 having a number average molecular weight of 2000 were obtained.
Part, hydride of alcohol-modified dicyclopentadiene polymer (number average molecular weight 590, hydroxyl value 190 mgKOH
/ G) 134.0 parts were charged and mixed and dissolved at 110 ° C. for 1 hour under a nitrogen stream. Then, after cooling to 85 ° C., 243.9 parts of isophorone diisocyanate was charged and reacted at 85 ° C. for 5 hours to obtain 750 parts of an isocyanate group-terminated urethane prepolymer. The urethane prepolymer was cooled to 70 ° C. 1225 parts of water,
225 parts isopropyl alcohol, 4 triethylamine
The urethane prepolymer was added and dispersed under stirring in an aqueous solution consisting of 0.5 part and 52.6 parts of adipic acid dihydrazide, and reacted at 50 ° C. for 3 hours. The thus obtained aqueous dispersion of polyurethane resin had a resin solid content concentration of 35%, a viscosity of 600 mPa · s / 25 ° C. and a pH of 8.0.

Comparative Example 1 A reaction vessel equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introducing tube was charged with 59.4 parts of dimethylolbutanoic acid and 489.9 parts of polypropylene glycol having a number average molecular weight of 2000, under a nitrogen stream. The mixture was mixed and dissolved at 110 ° C. for 1 hour. Then, after cooling to 85 ° C., 200.8 parts of isophorone diisocyanate was charged and reacted at 85 ° C. for 5 hours to obtain 750 parts of an isocyanate group-terminated urethane prepolymer. 7 parts of this urethane prepolymer
Cooled to 0 ° C. The urethane prepolymer was added to and dispersed in an aqueous solution of 1208 parts of water, 225 parts of isopropyl alcohol, 40.5 parts of triethylamine, and 43.3 parts of adipic acid dihydrazide with stirring, and the mixture was heated to 50 ° C.
Was reacted for 3 hours. The aqueous dispersion of polyurethane resin thus obtained has a resin solid content concentration of 35% and a viscosity of 500 m.
It was Pa · s / 25 ° C. and pH 8.0.

Each of the polyurethane resin aqueous dispersions obtained in Example 1 and Comparative Example 1 was evaluated for the following items. The results are shown in Table 1.

Adhesion: Each polyurethane resin aqueous dispersion is
Corona treated polypropylene film (OP
P), polyethylene terephthalate film (PE
T) and a nylon film (NY) treated surface were coated with a bar coater (No. 4) and then dried with a heat gun for 1 minute to obtain a polyurethane resin coating film. Next, an adhesive tape was attached to the coated surface, and the remaining condition of the coating film when peeled off in the direction perpendicular to the coated surface was visually evaluated. ◯: No peeling occurred. Δ: 50% or more remained. X: Less than 50% remained.

Blocking resistance: A mixture of the following compositions was kneaded with a paint shaker to prepare a blue printing ink. Phthalocyanine blue 15 parts Aqueous dispersion of polyurethane resin 50 parts Isopropyl alcohol 5 parts Ion-exchanged water 30 parts Commercially available oriented polypropylene (OPP) film, these indigo printing inks are spread with a bar coater (No. 6), It was dried with a heat gun for 30 seconds. After drying, a stretched polypropylene film on which no ink has been spread is attached to the ink surface of each of the spread products, and 0.5 MPa is applied.
After being left at 50 ° C. for 15 hours under a load of 1, the film was peeled off and the judgment was made according to the following criteria. The results are shown in Table 2. ◯: The films peeled off without resistance. Δ: There is resistance when the films are peeled from each other, but the ink does not transfer to the film on the side where the color is not spread. X: There is resistance when the films are peeled off, and the ink is partially transferred to the film on the side where the color is not spread.

[0045]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA07 CA04 CA15 CA17 CA22                       CB03 CB04 CB05 CB07 CB08                       CC03 CC08 CC23 CC26 CC33                       CC34 CC45 CC52 CC61 CC62                       DA01 DB03 DB07 DF01 DF02                       DF20 DF22 DG03 DG04 DG06                       DG16 DP03 DQ09 HA01 HA07                       HC03 HC12 HC13 HC17 HC22                       HC46 HC52 HC61 HC64 HC67                       HC71 HC73 JA03 JA13 QC05                       RA07                 4J039 AD18 AE04 AF07 BC03 BC04                       BC07 BC08 BC12 BC16 BC18                       BC22 BC23 BC36 BC54 CA06

Claims (7)

[Claims] 1. An aqueous polyurethane resin obtained by reacting a high molecular weight polyol, a hydride of a petroleum resin having active hydrogen, and a polyisocyanate compound as main components. 2. The aqueous polyurethane resin according to claim 1, wherein the hydride of a petroleum resin having active hydrogen is a hydride of an alcohol-modified dicyclopentadiene resin. 3. The weight ratio of the hydride of petroleum resin having active hydrogen to the high molecular weight polyol is 1/99 to.
70/30, The water-based polyurethane resin according to any one of claims 1 and 2. 4. The aqueous polyurethane resin according to claim 1, wherein the high molecular weight polyol is a water-soluble polyol. 5. The aqueous polyurethane resin according to claim 1, which has an ionic functional group. 6. A printing ink binder using the aqueous polyurethane resin according to claim 1. 7. A printing ink composition comprising the binder for printing ink according to claim 6.