JP2002284984A - Polyurethane resin solution, binder for printing ink, binder for coating material and binder for adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin solution hardly causing change of general constants with time such as a viscosity and a molecular weight, and having stable qualities, and further to provide a binder for a printing ink, a binder for a coating material and a binder for an adhesive by using the resin solution. SOLUTION: This polyurethane resin solution contains 0.0001-0.5 wt.% phosphoric acid ester represented by general formula: (RO)n P(O) (OH)3-n (expressed in terms of solid of the polyurethane resin). This binder for the printing ink, the binder for the coating material and the binder for the adhesive contain the polyurethane resin solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin solution having a stable quality with almost no change over time in general constants such as viscosity and molecular weight, and a binder for printing ink and a coating material using the resin solution. The present invention relates to a binder and a binder for an adhesive.

[0002]

2. Description of the Related Art Polyurethane resin solutions are used in various applications such as printing inks, paints and adhesives because they have both flexibility and toughness and are excellent in adhesiveness. However, the stability over time of the solution is not sufficient, especially when acetates are used as the main solvent, various exchange reactions tend to occur between the acetates and the resin, and as a result, the molecular weight of the resin is reduced. And the viscosity tends to decrease, and the quality becomes unstable. This tendency was remarkable when the polyurethane resin had an amine value. In addition, in plastic film applications for printing and packaging, strict quality control is being carried out with the complexity of packaging contents and the advancement of packaging technology. If the viscosity is reduced, serious quality claims may be caused. Polyurethane resins have been awarded prizes in the fields of paints and adhesives. However, in these fields, the trend of sophistication and complexity has been remarkable, and there is the same demand as in the above-mentioned applications for printing and packaging plastic films.

[0003]

SUMMARY OF THE INVENTION The present invention provides a polyurethane resin solution having a stable quality with little change over time in general constants such as viscosity and molecular weight, and a binder for printing ink using the resin solution. The present invention relates to a binder for a paint and a binder for an adhesive.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, by adding a specific phosphorus compound to a polyurethane resin solution, all of the above problems have been solved. The inventors have found that the present invention can be performed, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula: (RO)_nP
(O) (OH)_3-n  The phosphoric acid ester represented by 0.0001 to 0.5 weight
% (Polyurethane resin solid content equivalent)
It relates to a urethane resin solution. The present invention also provides the polyurethane
Printing ink binder using a tongue resin solution,
The present invention relates to a binder for a paint and a binder for an adhesive.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Phosphate used in the present invention
Is represented by the general formula (1): (RO)_nP (O) (OH)_3-n  (Wherein, R represents an alkyl group having 1 to 30 carbon atoms, and n represents
Shows an integer of 1 to 3. ).

The polyurethane resin solution used in the present invention is not particularly limited, and various known polyurethane resin solutions can be used. The polyurethane resin is generally obtained by reacting a polymer polyol, a diisocyanate compound, a chain extender and, if necessary, a chain terminator.

Examples of the polymer polyol used for producing the polyurethane resin solution 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, 2-methyl-1,3-propanediol, neopentyl glycol, pentanediol, 3-methyl- 1,
Various known or low-molecular saturated or unsaturated glycols such as 5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butynediol, and dipropylene glycol, or n-butyl glycidyl 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, and oxalic acid Polyester polyols obtained by dehydrating and condensing an acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid and other dibasic acids or their corresponding acid anhydrides and dimer acids; cyclic esters Polyester polyols obtained by ring-opening polymerization of compounds; other polycarbonate polyols, polybutadiene glycols, and glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A; Various known polymer polyols, and the like.

[0009] In the case of a high molecular polyol obtained from a glycol and a dibasic acid among the high molecular polyols, up to 5 mol% of the glycol can be replaced by the following various polyols. For example, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol and the like can be mentioned.

The number average molecular weight of the high molecular polyol is as follows:
It is appropriately determined in consideration of the solubility, drying property, and the like of the obtained polyurethane, and is usually about 700 to 10,000, preferably 1,000 to 6,000. If the number average molecular weight is less than 700, the solubility tends to decrease and the resin tends to precipitate at low temperatures, and if it exceeds 10,000, the drying property of the coating tends to decrease.

As the diisocyanate compound used for the production of the polyurethane resin, 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, hydrogen Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, Cyclohexyl-4,4 '
-Diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate, m-tetramethylxylylene diisocyanate, dimer isocyanate in which a carboxyl group of dimer acid is converted into an isocyanate group, and the like.

As the chain extender used for producing the polyurethane resin, various known agents can be used. For example, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like can be mentioned. In addition, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2
Diamines having a hydroxyl group in a molecule thereof such as -hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine, and dimers obtained by converting carboxyl groups of dimer acids into amino groups; Diamines and the like are also typical examples.

Further, examples of the chain terminator used as required include, for example, mono-n-butylamine and di-n-butylamine.
Examples thereof include alkylamines such as butylamine and alkanolamines such as monoethanolamine and diethanolamine.

As a method for producing the polyurethane resin, first, a polymer polyol and a diisocyanate compound are reacted under an isocyanate group excess condition to prepare a prepolymer having an isocyanate group at the terminal of the polymer polyol. In a suitable solvent with a chain extender and, if necessary, a polymerization terminator, and a polymer polyol, a diisocyanate compound, a chain extender and, if necessary, a polymerization terminator in a suitable solvent. Any one-step method of reacting at once can be employed, but the former method is preferred for the purpose of obtaining a uniform polymer solution. In these production methods, the solvent used is not limited, and aromatic solvents such as toluene and xylene; acetates such as ethyl acetate and butyl acetate; alcohol solvents such as methanol, ethanol, isopropanol and n-butanol; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be used alone or as a mixture. Particularly, acetate esters are preferably used as the main solvent from the viewpoints of solubility, toxicity, economy and the like of the polyurethane resin.

When the polyurethane resin is produced by the two-step method, the conditions for reacting the prepolymer with the chain extender and, if necessary, the polymerization terminator are not particularly limited. When the isocyanate group of the formula (1) is 1 equivalent, the total equivalent of the active hydrogen capable of reacting with the isocyanate group in the chain extender is preferably in the range of 0.5 to 2 equivalents. When the amount of the active hydrogen is less than 0.5 equivalent, the drying property of the film is not sufficient, and when the amount of the active hydrogen exceeds 2 equivalents, the chain extender may remain unreacted. Not preferred. In particular, considering the use as a binder for printing ink, which is strongly required to have adhesion to various plastic films, 1.0
It is preferable to adjust so as to be in the range of 1 to 2.0 equivalents, and to have an amine value of 0.2 to 20 per solid content of the polyurethane resin.

The number average molecular weight and weight average molecular weight of the polyurethane resin are appropriately determined in consideration of the drying property of the obtained resin film, the viscosity of the solution, and the like.
It is good to be in the range of 100,000 and 10,000 to 500,000.

The resin solids concentration of the polyurethane resin solution of the present invention is not particularly limited, but may be appropriately determined in consideration of workability and the like, and is usually about 15 to 60% by weight, and the viscosity is 50 to 100000 mPa. Adjustment to the range of about s / 25 ° C. is practically preferable.

The amount of the phosphate ester to be added to the polyurethane resin solution is 0.0001 to 0.5% by weight (in terms of the solid content of the resin). The compounding amount is 0.000
If the amount is less than 1% by weight, a sufficient stabilizing effect on the polyurethane resin solution cannot be exerted. If the amount exceeds 0.5% by weight, the phosphate ester contained in the resin film after coating is not enough. It easily migrates to the surface, and as a result, the adhesive strength of the film to the base plastic tends to decrease. The method of adding the phosphate ester is not particularly limited, but is most preferably added to the polyurethane resin solution after the reaction in order to prevent the effect of the present invention from being reduced by a side reaction between the phosphate ester and the polyurethane resin. When a phosphate ester is added during the production of the polyurethane resin, it is preferable to select conditions under which the phosphate ester does not cause a side reaction with the polyurethane resin. Specifically, when the production of a polyurethane resin is a two-step reaction, a polymer polyol and a diisocyanate compound are reacted under an isocyanate group excess condition to prepare a prepolymer having an isocyanate group at a terminal of the polymer polyol. Stage to do
And / or then the prepolymer may be added at a stage in which it is reacted with a chain extender and, if necessary, a polymerization terminator in a suitable solvent. When the production of the polyurethane resin is performed by a one-step reaction, a polymer polyol, a diisocyanate compound, a chain extender and, if necessary, a polymerization terminator can be added at a stage of reacting at once in a suitable solvent. .

The effect of the addition of the phosphoric acid ester is effectively exerted on various polyurethane resin solutions, but the effect is particularly remarkable on polyurethane resin solutions having an amine value of about 0.2 to 20. .

The polyurethane resin solution of the present invention obtained as described above contains a colorant, a solvent, and, if necessary, a surfactant, a wax and other additives for improving fluidity and surface film properties. The printing inks, paints, adhesives, etc. can be manufactured by appropriately compounding and kneading the compounds using a normal manufacturing apparatus such as various mills.

[0021]

According to the present invention, it is possible to provide a polyurethane resin solution having stable quality with almost no change over time in general constants such as viscosity and molecular weight. Further, it is possible to provide a binder for a printing ink, a binder for a paint, and a binder for an adhesive, which use the polyurethane resin solution and have excellent performances.

[0022]

EXAMPLES The present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts and% are based on weight.

Production Example 1 1000 parts of poly (1,4-butylene adipate) glycol having a molecular weight of 2,000 and 222 parts of isophorone diisocyanate were charged into a reactor equipped with a stirrer, a thermometer, and a nitrogen gas introducing tube, and 100 parts of nitrogen were fed under a nitrogen stream. The mixture was reacted at 6 ° C. for 6 hours to obtain a prepolymer having a free isocyanate value of 3.44%, and 523 parts of ethyl acetate was added thereto to obtain a uniform urethane prepolymer solution. Next, 73.8 parts of isophoronediamine, 16.9 parts of di-n-butylamine, 1518 parts of ethyl acetate and isopropyl alcohol 102
In the presence of 0 parts of the mixture, 1745 parts of the urethane prepolymer solution was added and reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 800 mPa · s / 25 ° C.
The amine value per resin solid content was 0 mgKOH / g.

Production Example 2 Isophorone diamine 8 was placed in the same reactor as in Production Example 1.
1.4 parts, 10.9 parts of di-n-butylamine, 1520 parts of ethyl acetate and 1021 parts of isopropyl alcohol were charged, and 1745 parts of the urethane prepolymer solution synthesized in Production Example 1 was added, followed by reaction at 50 ° C. for 3 hours. I let it. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 1000 mPa · s / 25.
C., the amine value per resin solid content was 2 mg KOH / g.

Production Example 3 Isophoronediamine 10 was placed in the same reactor as in Production Example 1.
7.7 parts, 1.4 parts of di-n-butylamine, 1547 parts of ethyl acetate and 1035 parts of isopropyl alcohol were charged, and 1745 parts of the urethane prepolymer solution synthesized in Production Example 1 was added, followed by reaction at 50 ° C. for 3 hours. I let it.
The polyurethane resin solution thus obtained had a resin solid content concentration of 30%, a viscosity of 1500 mPa · s / 25 ° C., and an amine value per resin solid content of 12 mgKOH / g.

Production Example 4 Poly (1,4-butylene adipate) glycol 100 having a number average molecular weight of 2000 was placed in the same reactor as in Production Example 1.
0 parts, 222 parts of isophorone diisocyanate and 0.44 part of dimethyl phosphate, and 6 parts at 100 ° C. under a nitrogen stream.
The mixture was reacted for a period of time to obtain a prepolymer having a free isocyanate value of 3.44%, and 523 parts of ethyl acetate was added thereto to obtain a uniform urethane prepolymer solution. Next, 81.4 parts of isophorone diamine, 10.9 parts of di-n-butylamine,
1520 parts of ethyl acetate and isopropyl alcohol 10
In the presence of 21 parts of the mixture, 1745 parts of the urethane prepolymer solution was added and reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 950 mPa · s / 25.
° C, amine value was 0.6 mgKOH / mg.

Examples 1 to 8 and Comparative Examples 1 to 3 To each of the polyurethane resins produced in Production Examples 1 to 3, phosphate esters were added as shown in Table 1 (Examples 1 to 8).
7). Since the phosphoric acid ester was used in the polyurethane resin of Production Example 4 at the time of production, no phosphate ester was added thereafter (Example 8). In Comparative Examples 1 to 3, no phosphate ester was added.

[0028]

[Table 1]

(Evaluation of Performance) Quality Stability For each of the polyurethane resin solutions shown in the above Examples and Comparative Examples, the viscosity (m) was measured immediately after preparation and after standing at 40 ° C. for 30 days.
Pa · s / 25 ° C.) and the weight average molecular weight (Mw) (in terms of polystyrene) determined by GPC measurement and compared. The rate of change was used as a measure of the quality stability of these polyurethane resin solutions. Table 2 shows the results.

[0030]

[Table 2]

(2) Evaluation of Adhesion Preparation of Print Film The polyurethane resin solutions obtained in the above Examples and Comparative Examples were kneaded with a paint shaker with the following composition to obtain a white printing ink. Use those inks at a plate depth of 30 μm
Thickness 1 with a simple gravure printing machine equipped with a gravure plate
Discharge treated surface of corona discharge treated OPP of 5 μm, thickness 11
The printed film was obtained by printing on one surface of PET having a thickness of μm and the discharge-treated surface of a nylon having a corona discharge treatment having a thickness of 15 μm and drying at 40 to 50 ° C. (Ink composition) Titanium oxide 30 parts Polyurethane resin solution 40 parts Ethyl acetate 20 parts Isopropyl alcohol 10 parts

Evaluation Method / Criteria After leaving the printed matter for one day, a cellophane tape was stuck on the printed surface, and the appearance of the printed film when this was rapidly peeled was observed and evaluated according to the following criteria. Table 3 shows the evaluation results. A: No peeling occurred. 〇: 80% or more of the printed film remained on the film. Δ: 50 to 80% or more of the printed film remained on the film. X: 50% or less of the printed film remained on the film.

[0033]

[Table 3]

Continued on the front page F term (reference) 4J002 CK021 EW046 FD206 GH01 GJ01 HA05 4J038 DG001 DG051 DG081 DG111 DG131 DG271 DG281 GA09 JA54 JC22 KA06 MA06 NA26 4J039 AE04 BC56 EA44 GA03 4J040 EF001 EF051 EF08 EF051

Claims (6)

[Claims] 1. The general formula: (RO)_nP (O) (OH)
_3-n  (Wherein, R represents an alkyl group having 1 to 30 carbon atoms, and n represents
Shows an integer of 1 to 3. )
0.0001 to 0.5% by weight (solid content of polyurethane resin
(Conversion) Polyurethane resin solution containing. 2. The polyurethane resin solution according to claim 1, wherein the main solvent of the polyurethane resin solution is an acetate. 3. The polyurethane resin solution according to claim 1, wherein the amine value per solid content of the polyurethane resin is 0.2 to 20. 4. A printing ink binder comprising the polyurethane resin solution according to claim 1. 5. A paint binder comprising the polyurethane resin solution according to claim 1. 6. An adhesive binder comprising the polyurethane resin solution according to claim 1.