JP2003313390A - Aqueous resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous resin composition exhibiting excellent water resistance ranking with that of a solvent-type urethane resin and excellent adhesion to a polyolefin film despite of its being an aqueous resin composition. <P>SOLUTION: The aqueous resin composition comprises as main components a resin emulsion (A) obtained by emulsifying a hydrogenate of an alicyclic hydrocarbon resin bearing a polar group in the presence of an emulsifier and an aqueous polyurethane resin (B). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous resin composition. The aqueous resin composition is a coating material for various binders such as paints and printing inks, plastics, glass, fibers, glass fibers, paper, wood, metal, rubber, synthetic leather, non-woven fabrics, concrete, etc.・ Can be used as an adhesive.

[0002]

2. Description of the Related Art Polyurethane resin has both flexibility and toughness and has excellent physical properties such as adhesiveness, chemical resistance, and abrasion resistance, and various binders, various coating agents, and various adhesives. -Used as an adhesive. Conventionally, polyurethane resin has been mainly used as a solvent type dissolved in an organic solvent, but in recent years, it has a low impact on the global environment, is excellent in the safety and hygiene of the working environment, and is suitable for resource conservation. From the standpoint of the above, conversion to water-based polyurethane resin is in progress.

However, since the water-based polyurethane resin is water-based, it has low water resistance as compared with the solvent-type polyurethane resin and has excellent adhesiveness to a relatively polar substrate such as polyethylene terephthalate or nylon. However, the adhesive strength to polyolefin films such as polyethylene films and polypropylene films, which are general-purpose films, is insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention is an aqueous resin composition having excellent water resistance which is not inferior to that of a solvent-type polyurethane resin and excellent adhesiveness to a polyolefin film, even though it is an aqueous resin composition. The purpose is to provide things.

[0005]

The present inventor has conducted extensive studies to solve the above-mentioned problems of the prior art, and as a result, an aqueous resin composition containing a mixture of an aqueous polyurethane resin and a specific resin emulsion as a main component. Have found that they can solve all the problems of the prior art, and have completed the present invention.

That is, the present invention contains a resin emulsion (A) obtained by emulsifying a hydride of an alicyclic hydrocarbon resin having a polar group in the presence of an emulsifier and an aqueous polyurethane resin (B) as main components. The present invention relates to a water-based resin composition comprising: a printing ink binder using the water-based resin composition; and a printing ink composition containing the printing ink binder.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the aqueous resin composition of the present invention, a resin emulsion (A) obtained by emulsifying a hydride of an alicyclic hydrocarbon resin having a polar group in the presence of an emulsifier (hereinafter, ( Component A) is essential.
The component (A) is composed of a hydride of an alicyclic hydrocarbon resin having a polar group, an emulsifier and water. The hydride of an alicyclic hydrocarbon resin having a polar group (hereinafter referred to as the component (a)), which is an essential constituent raw material of the component (A), contains an alicyclic compound as a main component and has a polar group in the resin molecule. A hydride having a group can be used without particular limitation. Also,
The manufacturing method of the component (a) is also not particularly limited. The component (a) can be obtained, for example, by modifying an alicyclic hydrocarbon resin with a polar group-containing compound when polymerizing an alicyclic compound to produce an alicyclic hydrocarbon resin. As the polar group in the component (a), a hydroxyl group, a carboxyl group, an amino group and the like can be mentioned, but the hydroxyl group is particularly preferable from the viewpoint of color tone, odor and the like.

Examples of the alicyclic compound constituting the component (a) include dicyclopentadiene and cyclopentadiene in the C5 fraction obtained by thermal decomposition of naphtha.

Examples of the polar group-containing compound constituting the component (a) include alcohol compounds. Specific examples of the alcohol compound include alcohol compounds having a double bond such as allyl alcohol. The polar group-containing compound may be used alone or in combination of two or more kinds. The hydroxyl group can also be introduced by a method of reducing the ester group introduced into the alicyclic hydrocarbon resin.

Further, the introduction of a hydroxyl group into an alicyclic hydrocarbon resin is carried out by leaving or introducing a double bond in the alicyclic hydrocarbon resin, and then hydrating the double bond. After thermally polymerizing vinyl carboxylate such as vinyl acetate to introduce an acyloxy group into the alicyclic hydrocarbon resin,
It can also be produced by a method of hydrolyzing the acyloxy group.

In the present invention, as the component (a), those obtained by the above-mentioned various methods can be used, but hydroxyl group-containing dicyclopentadiene obtained by copolymerizing dicyclopentadiene and allyl alcohol by thermal polymerization or the like. System resins (for example, JP-A-50-132060),
It is preferable because it is easy to control the hydroxyl value that contributes to the adhesiveness. The hydroxyl group-containing dicyclopentadiene-based petroleum resin is usually produced by copolymerizing about 10 to 200 parts by weight of an alcohol compound with 100 parts by weight of dicyclopentadiene.

Hydrogenation in the production of the component (a) is carried out by reacting an alicyclic hydrocarbon resin having a polar group with hydrogen in the presence of a hydrogenation catalyst, but the hydrogenation conditions should be adjusted appropriately. Is important. That is, the decomposition reaction of the polar group contained in the alicyclic hydrocarbon resin having a polar group is suppressed to be low, the obtained hydride becomes a light color, and the hydride is a resin emulsion described later. In some cases, the hydrogenation conditions must be appropriately determined in consideration of compatibility with the aqueous polyurethane resin (B). Generally, it is preferable to hydrogenate the alicyclic hydrocarbon resin having a polar group so that the content of the olefinic double bond is 1% or less. If the hydrogenation is such that the content of olefinic double bonds exceeds 1%, decolorization may be insufficient.

As the hydrogenation catalyst, various ones such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, rhenium and molybdenum or metal compounds such as oxides and sulfides thereof can be used. Further, such a hydrogenation catalyst may be used by supporting it on a carrier such as alumina, silica (diatomaceous earth), carbon, titania or the like which is porous and has a large surface area. Among these hydrogenation catalysts, the nickel-diatomaceous earth catalyst containing an alkaline earth metal is preferable because the hydrogenation rate can be easily adjusted within the above range and an excellent color tone can be obtained. As such a hydrogenation catalyst, for example, nickel-diatomaceous earth catalyst (“SN-2
50 ", manufactured by Sakai Chemical Co., Ltd., and the like. The hydrogenation catalyst is used in an amount of about 0.1 to 3% by weight of the alicyclic hydrocarbon resin having a polar group as a raw material resin, preferably 0.2 to
It is 2% by weight.

The hydrogenation reaction is usually carried out at a hydrogenation pressure of 3
-30 MPa range, reaction temperature is usually 200-30
The temperature is adjusted appropriately in the range of about 0 ° C. The hydrogenation pressure is preferably 10 to 20 MPa, and the reaction temperature is 200 to
It is 300 ° C. When the hydrogenation pressure is less than 3 MPa, hydrogenation is difficult to proceed, and when it exceeds 30 MPa, there is a problem in equipment. Further, when the reaction temperature is less than 200 ° C., it is difficult to lighten the hydride obtained,
If the temperature exceeds ℃, decomposition tends to occur and the softening point tends to decrease. The reaction time is usually about 1 to 7 hours, preferably 2 to 6 hours. The hydrogenation reaction is performed in a state where the alicyclic hydrocarbon resin having a polar group is melted or dissolved in a solvent. As the solvent, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran,
Isopropyl alcohol or the like can be used.

Regarding the amount of the catalyst used and the reaction time, the batch type was used as the reaction type, but the flow type (fixed bed type, fluidized bed type, etc.) may be used as the reaction type. it can.

The polar group content of the component (a) thus obtained is not particularly limited, but when the polar group is a hydroxyl group, the hydroxyl value is about 20 to 250. preferable. Since the compatibility with the aqueous polyurethane resin (B) tends to decrease as the hydroxyl value decreases, the hydroxyl value is more preferably 30 or more. Further, when the hydroxyl value increases, the molecular weight tends to decrease and workability tends to deteriorate, so the hydroxyl value is more preferably 200 or less.

The softening point of the component (a) is usually 70-15.
It is about 0 ° C. When the softening point is low, blocking occurs and the workability is deteriorated. Therefore, the lower limit of the softening point is more preferably 80 ° C. On the other hand, when the softening point is high, the compatibility with the aqueous polyurethane resin (B) tends to be poor, so the upper limit of the softening point is more preferably 140 ° C.

The average molecular weight of the component (a) is not particularly limited, but generally, the number average molecular weight is preferably about 100 to 600. When the number average molecular weight is small, the softening point is low and the workability tends to be poor. Therefore, the number average molecular weight is more preferably 200 or more. On the other hand, since the compatibility with the aqueous polyurethane resin (B) tends to decrease as the number average molecular weight increases, the number average molecular weight is 4
It is more preferably set to 00 or less. The number average molecular weight is determined by gel permeation chromatography (GPC).
According to polystyrene conversion value by method.

The component (a) is generally a light color, and usually has a color tone of about 3 or less of Gardner. When the color tone is particularly important in the use of the finally prepared aqueous resin composition, the color tone of the component (a) is preferably Gardner 2 or less, and more preferably Gardner 1 or less.

Various known anionic and / or nonionic emulsifiers can be used as the emulsifier which is an essential constituent raw material of the component (A). Examples include α-olefin sulfonates, alkyl sulphates, alkyl phenyl sulphates, polyoxyethylene alkyl phenyl ether sulphates, polyoxyethylene alkyl phenyl ether sulphosuccinic acid half ester salts, polyoxyethylene alkyl sulphosuccinic acid metal salts, rosin soaps. Examples thereof include anionic emulsifiers such as, and nonionic emulsifiers such as polyoxyethylene alkylphenyl ether. These can be used alone or in admixture of two or more.

The amount of the emulsifier used is not particularly limited, but is usually about 1 to 10 parts by weight, preferably 2 to 7 parts by weight in terms of solid content, relative to 100 parts by weight of the component (a). If it exceeds 10 parts by weight, the water resistance of the resulting aqueous resin composition may be lowered, and if it is less than 1 part by weight, the storage stability of the resin emulsion during emulsification may be deteriorated.

The method of emulsifying the component (a) is not particularly limited,
Any known emulsification method such as a high-pressure emulsification method, an inversion emulsification method, an ultrasonic emulsification method, and a solvent emulsification method may be adopted. For example, when the high-pressure emulsification method is adopted, the hydride is dissolved in a solvent such as benzene and toluene, the emulsifier and soft water are added, and the mixture is emulsified using a high-pressure emulsifier under a pressure condition of about 10 to 50 MPa. After that, the solvent may be removed under reduced pressure.

The solid content concentration of the component (a) thus obtained is not particularly limited, but it is usually adjusted appropriately so as to be about 20 to 70% by weight and used. The average particle size of the obtained emulsion is usually about 0.2 to 2 μm, and most of them are uniformly dispersed as particles of 0.5 μm or less. Also, the emulsion has a white appearance and
It has a pH value of ~ 9.

The aqueous resin composition of the present invention is a composition comprising the component (A) and the aqueous polyurethane resin (B). The water-based polyurethane resin (B) is not particularly limited, and various known water-based polyurethane resins are applicable. The aqueous polyurethane resin (B) is generally obtained by reacting a polymer polyol, a diisocyanate compound, a chain extender and, if necessary, a chain length terminating agent. As the polymer polyol used for producing the aqueous polyurethane resin (B), for example, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran and the like; ethylene glycol, diethylene glycol, triethylene and the like. Ethylene 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 saturated and unsaturated low molecular weight glycols or n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether and other alkyl glycidyl ethers , Monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, dimer diol obtained by reducing dimer acid, and adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid Polyester polyols obtained by dehydration condensation of dibasic acid such as acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or acid anhydride or dimer acid corresponding thereto; cyclic ester Polyester polyols obtained by ring-opening polymerization of compounds; other polycarbonate polyols, polybutadiene glycols, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, etc. are generally used for the production of aqueous polyurethane resins. each Known polymer polyols, and the like.

The number average molecular weight of the polymer polyol is
Although not particularly limited, it is usually in the range of about 500 to 10,000, preferably 700 to 6000. When the number average molecular weight is less than 700, the resulting aqueous resin composition film tends to be too hard, and when it exceeds 10,000, the drying property and blocking resistance tend to decrease.

As typical examples of the above-mentioned diisocyanate compound, various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1,
5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1 , 4-
Phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane- 1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate and dimer Dimerge isocyanate obtained by converting carboxyl group of acid to isocyanate group Over doors and the like.

A chain extender may be used in the production of the aqueous polyurethane resin (B). For example, various known low-molecular-weight polyols listed in the section of the description of the polyester diol; amines such as ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine. In the molecule of 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. Diamines having a hydroxyl group; dimer diamines obtained by converting the carboxyl group of dimer acid into amino groups, hydrazine, adipic acid dihydrazide, etc. are typical examples. Can be given as.

If necessary, a chain length terminator may be used. Examples of such chain length terminators are: The-
Examples include dialkylamines such as n-butylamine and monovalent alcohols such as ethanol and isopropanol.

The hydration means necessary for producing the aqueous polyurethane resin (B) is not particularly limited, and various known methods can be adopted. For example, 1) a method of using a water-soluble raw material, 2) a self-emulsification method, 3) a method of forcibly emulsifying a urethane resin in an emulsifier aqueous solution, and the like.

Examples of the method 1) include a method of using a raw material polyol with a water-soluble oligomer such as polyoxyethylene glycol as a part of the polymer polyol to make it water-soluble. The amount of the water-soluble oligomer used is not particularly limited, but when polyoxyethylene glycol is used, for example, it is usually appropriate to be about 20 to 80% by weight based on the solid content of the aqueous polyurethane resin (B).

As the method 2), there is a method of introducing an ionic group such as a quaternary amino base or a carboxylate group into the molecular chain to self-emulsify. In the method of introducing a quaternary amino base into a molecular chain, a chain extender containing at least one basic nitrogen, such as a mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic compound, is used. Primary amines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-isobutyldiethanolamine, N-oleyldiethanol -N-amine, N-stearyldiethanolamine, ethoxylated palm oil amine, N-allyldiethanolamine, N-methyldiisopropano-
Ruamine, N-ethyldiisopropanolamine, N-
Propyldiisopropanolamine, N-butyldiisopropanolamine, N-cyclohexyldiisopropanolamine, N, N-diethoxylaniline, N, N
-Diethoxytoluidine, N, N-diethoxyl-1
-Aminopyridine, N, N'-diethoxylpiperazine, dimethyl-bis-ethoxylhydrazine, N, N '
-Bis- (2-hydroxyethyl) -N, N-diethylhexahydro-p-phenylenediamine, N-12-hydroxyethylpiperazine, polyalkoxylated amines, such as propoxylated methyldiethanolamine,
N-methyl-N, N-bis-3-aminopropylamine, N- (3-aminopropyl) -N, N'-dimethylethylenediamine, N- (3-aminopropyl) -N-
Methylethanolamine, N, N'-bis- (3-aminopropyl) -N, N'-dimethylethylenediamine,
N, N'-bis- (3-amonopropyl) piperazine,
N- (2-aminoethyl) piperazine, N, N'-bisoxyethylpropylenediamine, 2,6-diaminopyridine, dietanolaminoacetamide, dietano-
Lamidopropionamide, N, N'-bisoxyethylphenylsemicarbazide, N, N-bisoxymethylsemicarbazide, p, p'-bis-aminomethyldibenzylmethylamine, 2,6-diaminopyridine, 2-dimethylamino Methyl-2-methylpropane-1,3-diol or the like is used and quaternized with a quaternizing agent such as an acid anion, for example, chloride, sulfate or organic carboxylate anion before or after dispersion in water. It In the method of introducing a carboxylate group into the molecular chain, a chain extender having at least one carboxyl group, glyceric acid,
Dioxymaleic acid, dioxyfumaric acid, tartaric acid, 2,
6-dioxybenzoic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,
2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, 4,4-bis (hydroxyphenyl) valeric acid,
Using 4,4-bis (hydroxyphenyl) butyric acid etc.,
When dispersed in water, alkali metals such as potassium hydroxide and sodium hydroxide, ammonia or trimethylamine, triethylamine, triethanolamine, N-alkyldiethanolamine, N, N'-dialkylmonoethanolamine and the like 3 Neutralized with primary amines. In addition, these chain extenders having ionicity can be used as a part of the glycols which are the constituent components of the polymer polyol. The content of these ionic groups is not particularly limited, but an acid value or amine value of about 2 to 100 is usually suitable per 1 g of the polyurethane resin solid content.

The method 3) is a method of mixing and emulsifying a urethane resin, a urethane prepolymer or the like in the presence of an emulsifier. As the emulsifier, various known emulsifiers can be used. Examples of the nonionic emulsifier include polyoxyethylene glycol ether of long chain alcohol, polyoxyethylene glycol ether of alkylphenol, and polyethylene glycol. There are block copolymers and the like of polypropylene and polypropylene glycol, and examples of the anionic type include sulfuric acid esters of long chain fatty acids, alkylallyl sulfonic acids, alkali metal salts of high molecular weight organic acids, ammonium salts, There are tertiary amine salts and the like, and as the cation type, there are quaternary ammonium salts and the like. The amount of these emulsifiers to be used is not particularly limited, but is usually 3 to 30% by weight based on the solid content of the polyurethane resin (B).

Among the methods 1) to 3), the method 2) is particularly preferable in that an aqueous polyurethane resin (B) having excellent dispersion stability and water resistance can be obtained.

The aqueous resin composition of the present invention contains the above component (A) and the aqueous polyurethane resin (B) as main components. The usage ratio (solid content weight ratio) is determined in consideration of the adhesiveness to various substrates such as a polyolefin film, and (A) / (B) is usually 1/99 to 7
It is set to 0/30, preferably 5/95 to 50/50.
When the ratio of the resin emulsion (A) is less than 1, almost no modification effect on various physical properties such as adhesiveness and water resistance is observed, and when it exceeds 70, the cohesive force tends to decrease.

The aqueous resin composition of the present invention obtained as described above contains a coloring agent and, if necessary, a surface active agent such as an antifoaming agent or a leveling agent for improving fluidity and surface film characteristics. , Other additives are appropriately blended, and a printing ink, a paint, a viscous / adhesive agent, etc. can be produced by kneading the mixture using a general production apparatus such as various mills.

[0036]

According to the present invention, the aqueous resin composition has excellent water resistance and further has polyethylene (PE)
It is possible to provide an aqueous resin composition having excellent adhesiveness to polyolefin films such as polypropylene and polypropylene (PP).

[0037]

EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples.

Production Example 1 (Production of hydride of alicyclic hydrocarbon resin having hydroxyl group) Among petroleum fractions, a so-called C5 fraction, a fraction mainly containing cyclopentadiene as a polymerizable monomer and allyl Alicyclic hydrocarbon resin having a hydroxyl group, which is obtained by thermal polymerization with alcohol (manufactured by Nippon Zeon Co., Ltd., trade name "Quinton 1700", softening point 100 ° C, number average molecular weight 30
0, color tone 7 Gardner, hydroxyl value 200) 100 parts,
1.0 part of a previously reduced nickel-diatomaceous earth catalyst (manufactured by Sakai Chemical Industry Co., Ltd., trade name "SN-250") was charged into an autoclave, hydrogen pressure was 19.6 MPa, reaction temperature was 2
The hydrogenation reaction was carried out under the conditions of 50 ° C. and reaction time of 5 hours. After completion of the reaction, the obtained resin was dissolved in 300 parts of toluene and filtered to remove the catalyst. Then, the filtrate was put into a 1-liter separable flask equipped with a stirring blade, a reflux condenser, a thermometer, a temperature controller and a pressure indicator, and the temperature was gradually raised to 200 kPa and depressurized to 2.7 kPa. The solvent was removed to obtain 98 parts of a hydride of an alicyclic hydrocarbon resin having a number average molecular weight of 280, a softening point of 101 ° C., a color tone of 100 Hazen, and a hydroxyl value of 80.

The softening point is determined by the ring and ball method of JIS K 2531. Also, in the case of Hazen color, the color tone is 5
After making a 0% toluene solution and visually comparing it with the Hazen standard color (H), the value is doubled (because it is diluted by 50%) and then judged.
Melted at 80 ℃, Gardner Standard Color (G)
It was visually determined by. The hydroxyl value was in accordance with JIS K0070.

Production Example 2 (Production of Resin Emulsion) 100 parts of the hydride obtained in Production Example 1 was mixed with 50 parts of toluene.
After dissolving in 100 parts at 100 ° C. for about 1 hour, it was cooled to 80 ° C. Next, as an emulsifier, anionic emulsifier (trade name "HITENOL S", solid content 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added in an amount of 3 parts in terms of solid content and 120 parts of water, and at 75 ° C for 1 hour Preliminary emulsification was performed with vigorous stirring. Further, the obtained preliminary emulsion was subjected to high pressure emulsification at a pressure of 30 MPa with a high pressure emulsifying machine (manton gaurin company) to obtain an emulsion. Then, charge the emulsion to a vacuum distillation apparatus,
Vacuum distillation was carried out under the conditions of 70 ° C. and 130 hPa for 6 hours to obtain a resin emulsion having a solid content of 50%.

Production Example 3 (Production of Aqueous Polyurethane Resin) A reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe was charged with 59.4 parts of dimethylolbutanoic acid and polypropylene glycol 489. 9
Parts were charged and mixed and dissolved at 110 ° C. for 1 hour under a nitrogen stream. Then, after cooling to 85 ° C., 200.8 parts of isophorone diisocyanate was charged and the mixture was heated to 85 ° C. for 5 hours.
The reaction was allowed to proceed for a period of time to obtain 750 parts of an isocyanate group-terminated urethane prepolymer. Then, 1208 parts of water, 225 parts of isopropyl alcohol, 40.
The urethane prepolymer was added and dispersed under stirring in an aqueous solution consisting of 5 parts and 43.3 parts of adipic acid dihydrazide, and reacted at 50 ° C. for 3 hours. The polyurethane resin aqueous dispersion thus obtained had a resin solids concentration of 35
%, The viscosity was 500 mPa · s / 25 ° C., and the pH was 8.0.

Example 1 32 parts of titanium white (rutile type), 13 parts of isopropyl alcohol, 20 parts of water, 30 parts of the aqueous polyurethane resin solution obtained in Production Example 3 and 5 parts of the resin emulsion obtained in Production Example 2 were used. The ingredients were blended and kneaded with a paint shaker to prepare a white printing ink.

Example 2 32 parts of titanium white (rutile type), 14 parts of isopropyl alcohol, 24 parts of water, 15 parts of the aqueous solution of the polyurethane resin obtained in Production Example 3, and 15 parts of the resin emulsion obtained in Production Example 2 were used. The ingredients were blended and kneaded with a paint shaker to prepare a white printing ink.

Example 3 32 parts of titanium white (rutile type), 13 parts of isopropyl alcohol, 18 parts of water, 36 parts of the polyurethane resin aqueous solution obtained in Production Example 3 and 1 part of the resin emulsion obtained in Production Example 2 were used. The ingredients were blended and kneaded with a paint shaker to prepare a white printing ink.

Comparative Example 1 32 parts of titanium white (rutile type), 13 parts of isopropyl alcohol, 18 parts of water, and 37 parts of the aqueous solution of the polyurethane resin obtained in Production Example 3 were blended and kneaded with a paint shaker to give a white printing ink. Was prepared.

The white printing inks obtained in Examples 1 to 3 and Comparative Example 1 were evaluated for the following items. The results are shown in Table 1.

Adhesion: White printing ink was applied to a corona-treated polypropylene film (OPP), polyethylene terephthalate film (PET), and nylon film (NY) on the treated and untreated surfaces with a bar coater (No. 4). Was used to develop the color, and then dried with a dryer for 1 minute to obtain a color-developed film. Then, an adhesive tape was attached to the ink surface of the color-developing film, and the remaining state of the ink film when peeled off in the direction perpendicular to the ink surface was visually evaluated. ◯: It did not peel at all. Δ: 50% or more of the printed film remained on the film. X: Less than 50% of the printed film remained on the film.

Water resistance: Each white printing ink was color-developed with a bar coater (No. 4) on the treated surface of NY subjected to corona treatment, and dried with a dryer for 30 seconds to obtain a color-developed film. Then, the spread film was immersed in hot water at 80 ° C., and the remaining condition of the ink film was visually evaluated. ◯: It did not peel at all. Δ: 50% or more of the printed film remained on the film. X: Less than 50% of the printed film remained on the film.

[0049]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 BK00W CE00W CK02X GH01                       GJ02 GT00 HA07                 4J039 AD16 AD19 AE04 BE01 BE02                       BE12 BE22 CA03 EA38 EA43

Claims (8)

[Claims] 1. An aqueous solution containing a resin emulsion (A) obtained by emulsifying a hydride of an alicyclic hydrocarbon resin having a polar group in the presence of an emulsifier and an aqueous polyurethane resin (B) as main components. Resin composition. 2. The aqueous resin composition according to claim 1, wherein the polar group of the hydride of the alicyclic hydrocarbon resin having a polar group is a hydroxyl group, and the hydroxyl value of the hydride is 20 to 250. 3. The aqueous resin composition according to claim 1 or 2, wherein the hydride of the alicyclic hydrocarbon resin having a polar group has a softening point of 70 to 150 ° C. 4. The aqueous resin composition according to claim 1, 2 or 3, wherein the color tone of the hydride of the alicyclic hydrocarbon resin having a polar group is Gardner 3 or less. 5. The aqueous resin according to claim 1, wherein the hydride of the alicyclic hydrocarbon resin having a polar group is obtained by hydrogenating an alicyclic hydrocarbon resin having a polar group. Composition. 6. A solid content weight ratio of (A) and (B) (A) /
(B) is 1/99 to 70/30, The aqueous resin composition of Claims 1-5. 7. A binder for a printing ink, which uses the aqueous resin composition according to claim 1. 8. A printing ink composition comprising the binder for printing ink according to claim 7.