JPH0668088B2 - Binder for printing ink - Google Patents

Description

The present invention relates to a binder for printing ink. (Problems to be solved by conventional techniques / inventions) In recent years, with the diversification of packaged items and the sophistication of packaging technology,
Various plastic films have been developed as a packaging material, and one suitable for a packaged item has been appropriately selected and used. By the way, when a plastic film is used as a packaging material, printing is performed for decoration or surface protection of the plastic film, and the printing ink for such printing has good adhesiveness to these various plastic films. There is an increasing demand for high performance such as certain features.

Polyurethane is often used as a binder for printing inks used for such printing inks that have been conventionally used. In general, printing inks using polyurethane as a binder have excellent adhesive strength alone to polyester films and nylon films, but since the adhesive strength to general-purpose films such as polyethylene film and polypropylene film is insufficient, polyethylene film When printing on a polypropylene film or a polypropylene film, a two-component reactive ink in which a polyisocyanate compound is mixed with polyurethane is used to supplement the adhesive force.

However, the two-component reactive ink has a disadvantage that it needs to be mixed with a curing agent immediately before printing, is inconvenient to handle, and has various practical limitations in terms of pot life (pot life). . Therefore, in this field, the adhesiveness to various plastic films is good,
In addition, various studies and developments have been conducted on polyurethanes that can be used as binders for one-component inks that do not require the addition of polyisocyanate compounds, and the adhesiveness has been improved to some extent. However,
For example, when the one-pack type ink is used for printing a plastic film used as a packaging base material that is subjected to a boil sterilization process, a retort sterilization process, etc. after packaging a food, such a printed material has a boil resistance and a retort resistance. Sex (hereinafter,
There is a problem that the boil resistance etc.) is still inferior.
Therefore, since it is difficult to use the one-pack type ink in the field where the boil resistance is required, the two-pack reactive ink in which the polyisocyanate compound is blended still occupies the mainstream although it has the drawbacks as described above. Is the current situation.

The present inventors have solved the above problems and provide a binder for a one-component printing ink having excellent adhesion to various plastic films such as polyester, nylon, polyethylene, and polypropylene as a material to be printed, and boil resistance. As a result of extensive studies aimed at that, when the polyurethane using the long-chain dibasic acid as the dibasic acid component of the polyester diol is used as the binder for the printing ink, the problems of the above-mentioned conventional techniques can be completely solved. This has led to the completion of the present invention.

(Means for Solving the Problems) That is, the present invention comprises a dibasic acid component containing at least 50% by weight of a dibasic acid having 20 to 28 carbon atoms and a glycol component, and a polyester having a number average molecular weight of 500 to 4000. Diols, diisocyanate compounds, and
The present invention relates to a printing ink binder, which mainly contains a polyurethane resin obtained by reacting a polyamine as a chain extender.

In the present invention, as means for solving the above problems, a polyester diol comprising a dibasic acid component containing at least 50% by weight of a dibasic acid having 20 to 28 carbon atoms and a glycol component is used. That is, in the present invention, the long-chain dibasic acid has an effect of improving boiling resistance and the like.

Here, a dibasic acid having 20 to 28 carbon atoms means a linear or branched saturated or unsaturated long-chain dibasic acid, among which a cyclo ring and / or an aromatic ring is contained in the molecule. Things are also included. If the carbon number is less than 20, it is not preferable because the boiling resistance is not improved. Specific examples of these include long-chain dibasic acids having 22 carbon atoms (trade name)
IPS-22, trade name IPU-22, Okamura Oil Co., Ltd., carbon number 20
Long-chain dibasic acid (trade name SL-20, trade name UL-20, trade name SB-20, trade name UB-
20, manufactured by Okamura Oil Co., Ltd., long-chain dibasic acid having 28 carbon atoms (trade name: ST-2P, manufactured by Okamura Oil Co., Ltd.) and the like.

Further, the long-chain dibasic acid is preferably contained in the dibasic acid component in an amount of at least 50% by weight. If it is less than 50% by weight, the boil resistance and the like are deteriorated when using a one-component ink. In addition,
Dibasic acid component of polyester diol is long-chain dibasic acid 10
Of course, it may be 0%.

In the present invention, in addition to the long-chain dibasic acid, various well-known compounds generally known as the acid component of polyester are used as the acid component of the polyester diol as long as they are in the range of less than 50% by weight in the dibasic acid component. Can be used together.
For example, dibasic acids such as adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid or the like. And acid anhydrides corresponding to. If the amount is less than 50% by weight, a dibasic acid having 16 carbon atoms (trade name SL-1
6. It is also optional to use UL-16, trade name of Okamura Oil Co., Ltd., dibasic acid having 12 carbon atoms (SL-12, trade name of Okamura Oil Co., Ltd.) and the like.

In addition, as the glycol which is another constituent component forming the long chain dibasic acid and the polyester diol of the present invention, 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-
Examples include various known saturated and unsaturated glycols such as pentanediol, hexanediol, octanediol, 1,4-butynediol and dipropylene glycol.

In addition, in the present invention, monoglycidyl ethers such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, phenylphenol glycidyl ether, and alkylphenyl glycidyl ether, versatic Monoglycidyl esters such as acid glycidyl ester, rosin glycidyl ester and glycidyl methacrylate, octylene oxide, styrene oxide, cyclohexene vinyl monooxide, α-pinene oxide, olefin oxide, diterpene oxide and other monooxides are also glycols of the present invention. Can be used as a kind of.

It should be noted that up to 5 mol% of the glycol component may be replaced with the following various polyols. That is, for example, glycerin, trimethylolpropane, trimethylolethane,
1,2,6-hexanetriol, 1,2,4-butanetriol,
Examples thereof include sorbitol and pentaerythritol.

The molecular weight of the polyester diol is appropriately determined in consideration of the solubility, drying property, blocking resistance, etc. of the polyurethane resin to be obtained, and is usually in the range of 500 to 4000. If the molecular weight is less than 500, the printability tends to be poor due to the decrease in solubility, while if it exceeds 4000, the drying property and blocking resistance tend to be reduced.

Further, within the range not deviating from the performance of the polyurethane resin, a part of the polyester diol component may be used by substituting it with a low molecular weight polyol, and the amount used in the polyol component is usually 20% by weight or less, Preferably
It is set to 10% by weight or less. Examples of the low molecular weight polyols include various low molecular weight polyols used for producing the high molecular weight polyols. When the use ratio of the low molecular weight polyol exceeds 20% by weight, the adhesiveness of the obtained printing ink composition to a plastic film and the solubility to a diluting solvent tend to decrease, which is not preferable.

Further, within the range not deviating from the performance of the polyurethane of the present invention, in addition to the above polyester diols, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran and the like, dibasic acid and glycol components. Polyester polyols other than the present invention obtained by condensing the above, polyester polyols obtained by ring-opening polymerization of a cyclic ester compound, other polycarbonate polyols, polybutadiene glycols, bisphenol A by adding ethylene oxide or propylene oxide Various known polymer polyols generally used in the production of polyurethane such as the obtained glycols can be used in combination.

In the present invention, as the 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, 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-
Typical examples thereof include bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimerisocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group.

Examples of the chain extender used in the present invention include ethylenediamine, propylenediaminehexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-
In addition to 4,4'-diamine, etc., 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-
Diamines having a hydroxyl group in the molecule such as hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine, and the low-molecular-weight glycols described in the above-mentioned polyester diol, oleic acid, linoleic acid, and the like. 36 carbon atoms obtained by dimerizing an unsaturated monocarboxylic acid having 18 carbon atoms
A typical example thereof is a polyamine such as a dimer diamine obtained by converting a carboxyl group of a dimer acid which is a polymer fatty acid containing the dicarboxylic acid as a main component into an amino group.

Furthermore, a chain length terminating agent can be used if necessary.
Examples of such chain length terminators include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol.

The method for producing the polyurethane used in the present invention is not particularly limited, but, for example, a polyester diol component and a diisocyanate compound are reacted under an excess of isocyanate groups to give a prepolymer having isocyanate groups at both ends of the polyester diol (preferably Is an isocyanate content of 0.5 to 10%) and then reacting this with a chain extender and, if necessary, a chain length terminating agent in a suitable solvent, as well as a polyester diol component, a diisocyanate compound and a chain extender. And, if necessary, any one-step method of reacting the chain length terminating agent in a suitable solvent at a time can be adopted, but the two-step method is adopted because it is easy to obtain a uniform polymer solution. preferable.

When the polyurethane resin used in the present invention is produced by the two-step method, the conditions for reacting the polyester diol component and the diisocyanate compound are not particularly limited, except that the isocyanate groups are excessive, but hydroxyl group / isocyanate It is preferable that the groups are reacted so that the equivalent ratio is in the range of 1 / 1.2 to 1/3. The conditions for reacting the obtained prepolymer with a chain extender and optionally a chain length terminating agent are not particularly limited, but 1 equivalent of a free isocyanate group at both ends of the prepolymer is used. When the total amount of active hydrogen capable of reacting with the isocyanate group in the chain extender is in the range of 0.5 to 2.0 equivalents, especially 0.5 to 1.3 equivalents when the active hydrogen-containing group is an amino group. It is preferably within the range. If the active hydrogen is less than 0.5 equivalents, the dryness, blocking resistance, film strength is not sufficient, the active hydrogen is
If the amount is more than 2.0 equivalents, the chain extender remains unreacted and odor tends to remain on the printed matter.

In these production methods, the solvent used is usually
Benzene, which is well known as a solvent for printing inks,
Aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate. These are used alone or as a mixture of two or more kinds.

The number average molecular weight of the polyurethane resin of the present invention obtained as described above is preferably in the range of 5,000 to 100,000. When the number average molecular weight is less than 5000, the drying property of the printing ink using this as a vehicle, blocking resistance,
The film strength, oil resistance, etc. tend to decrease, while 100,000
Polyurethane resin solution (binder)
The viscosity of the ink increases and the gloss of the printing ink tends to decrease. The concentration of the resin solid content of the polyurethane resin solution is not particularly limited, but may be appropriately determined in consideration of workability at the time of printing, and is usually 15 to 60% by weight, and the viscosity is 50 to 10%.
It is practically preferable to adjust the temperature within the range of 0000 cP / 25 ° C.

Further, in the present invention, in addition to polyurethane which is the main component of the present invention, the following resins may be used in combination as a binder of the present invention as an auxiliary component, if necessary. Examples thereof include polyurethanes, polyamides, nitrocelluloses, polyacrylic esters, polyvinyl chlorides, copolymers of vinyl chloride and vinyl acetate, rosin-based resins, and ketone resins other than those of the present invention.

A colorant, a solvent, a surfactant for improving ink fluidity and an ink surface film, if necessary, a wax, and other additives are appropriately blended in the binder of the present invention, and a usual ball mill, attritor, sand mill or the like is used. A printing ink composition can be produced by kneading with an ink producing device. The amount of the binder of the present invention in the printing ink composition is preferably such that the printing ink composition has a resin solid content of 3 to 20% by weight.

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

Production Example 1 1000 parts of long-chain dibasic acid (trade name ST-2P, Okamura Oil Co., Ltd.) and ethylenezol were placed in a round-bottomed flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas inlet tube. Esterification was carried out for 24 hours while charging 226 parts and removing condensed water at 200 ° C. under a nitrogen stream. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, hydroxyl value 111 KOH mg /
g, acid value 0.7 KOH mg / g, and 1087 parts of polyester polyol having a number average molecular weight of 1000 were obtained.

Production Example 2 A long-bottomed dibasic acid (trade name: IPS-22, manufactured by Okamura Oil Co., Ltd.) 1000 parts and 1,9 in a round bottom flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas inlet tube. -530 parts of nonanediol was charged and esterification was carried out for 24 hours while removing condensed water at 200 ° C under a nitrogen stream. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, the hydroxyl value is 35 KOH mg /
1362 parts of a polyester polyol having an acid value of 0.7 KOH mg / g and a number average molecular weight of 3000 were obtained.

Production Example 3 In a round-bottomed flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas inlet tube, 1000 parts of long-chain dibasic acid (trade name SL-20, manufactured by Okamura Oil Co., Ltd.) and 1,4 -Butanediol (351 parts) was charged, and esterification was performed for 24 hours while removing condensed water at 200 ° C under a nitrogen stream. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, hydroxyl value 54KOH mg /
1183 parts of a polyester polyol having an acid value of 0.2 KOH mg / g and a number average molecular weight of 2000 were obtained.

Production Example 4 In a round-bottomed flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas introduction tube, 600 parts of long-chain dibasic acid (trade name SL-20, manufactured by Okamura Oil Co., Ltd.) and adipic acid 400 And 335 parts of ethylene glycol were charged, and esterification was carried out for 24 hours while removing condensed water at 200 ° C. under a nitrogen stream. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, 1115 parts of a polyester polyol having a hydroxyl value of 56 KOH mg / g, an acid value of 0.3 KOH mg / g and a number average molecular weight of 2000 was obtained.

Production Example 5 A round bottom flask equipped with a stirrer, a thermometer, a water separator and a nitrogen gas inlet tube was charged with 1000 parts of adipic acid and 950 parts of 1,6-hexanediol and condensed water at 200 ° C under a nitrogen stream. The esterification was carried out for 24 hours with removal of. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, 1618 parts of a polyester polyol having a hydroxyl value of 57 KOH mg / g, an acid value of 0.2 KOH mg / g and a number average molecular weight of 2000 was obtained.

Production Example 6 In a round-bottomed flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas introduction tube, 1000 parts of long-chain dibasic acid (trade name SL-12, manufactured by Okamura Oil Co., Ltd.) and 1,9 -Nonanediol (802 parts) was charged, and esterification was carried out for 24 hours while removing condensed water at 200 ° C under a nitrogen stream. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, hydroxyl value 33KOH mg /
1563 parts of a polyester polyol having an acid value of 0.5 KOH mg / g and a number average molecular weight of 3000 were obtained.

Production Example 7 In a round-bottomed flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas introduction tube, 1000 parts of long-chain dibasic acid (trade name SL-16, manufactured by Okamura Oil Co., Ltd.) and ethylene glycol 310 A part was charged and esterification was carried out for 24 hours at 200 ° C. under a nitrogen stream while removing condensed water. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, hydroxyl value 115KOH mg /
1125 parts of a polyester polyol having an acid value of 0.4 KOH mg / g and a number average molecular weight of 1000 was obtained.

Production Example 8 The polyester polyol 1000 obtained in Production Example 1 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
And 333 parts of isophorone diisocyanate were charged and reacted under a nitrogen stream at 100 ° C. for 6 hours to produce a prepolymer having a free isocyanate content of 3.02%. Then, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of a urethane prepolymer. Then, 2148 parts of the urethane prepolymer solution was added to a mixture consisting of 75.4 parts of isophoronediamine, 9.1 parts of di-n-butylamine, 1390 parts of methyl ethyl ketone and 1103 parts of isopropyl alcohol, and then reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as "resin solution A") has a resin solid content concentration of 30.
%, The viscosity was 470 cp / 25 ° C. The number average molecular weight of the polyurethane resin was 34,000.

Production Example 9 The polyester polyol 1000 obtained in Production Example 2 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
Parts and 203 parts of m-tetramethylxylylene diisocyanate were charged and reacted under a nitrogen stream at 130 ° C for 6 hours to prepare a prepolymer having a free isocyanate content of 3.38%, and then 815 parts of methyl ethyl ketone was added to prepare a uniform solution of urethane prepolymer. And Then isophorone diamine
To a mixture of 76.8 parts, di-n-butylamine 8.3 parts, methyl ethyl ketone 1189 parts and isopropyl alcohol 1002 parts, was added the urethane prepolymer solution 2018 parts,
Then, the mixture was reacted at 50 ° C for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution B) had a resin solid content concentration of 30% and a viscosity of 780 cp / 25 ° C. The number average molecular weight of the polyurethane resin was 41,000.

Production Example 10 The polyester polyol 1000 obtained in Production Example 3 was placed in a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube.
And 222 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours in a nitrogen stream to produce a prepolymer having a free isocyanate content of 3.38%. Then, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of a urethane prepolymer. Then, 2037 parts of the urethane prepolymer solution was added to a mixture consisting of 78.1 parts of isophoronediamine, 8.4 parts of di-n-butylamine, 1220 parts of methyl ethyl ketone and 1018 parts of isopropyl alcohol, and then reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution C) has a resin solid content concentration of 30.
%, The viscosity was 720 cP / 25 ° C. The number average molecular weight of the polyurethane resin was 40,000.

Production Example 11 The polyester polyol 1000 obtained in Production Example 4 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
And 222 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours in a nitrogen stream to produce a prepolymer having a free isocyanate content of 3.40%. Then, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of urethane prepolymer. Then, 2037 parts of the urethane prepolymer solution was added to a mixture consisting of 78.6 parts of isophorone diamine, 8.4 parts of di-n-butylamine, 1221 parts of methyl ethyl ketone and 1018 parts of isopropyl alcohol, and then reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution D) has a resin solid content concentration of 30.
%, The viscosity was 1100 cp / 25 ° C. The number average molecular weight of the polyurethane resin was 39,000.

Production Example 12 The polyester polyol 1000 obtained in Production Example 5 was placed in a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube.
And 222 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours in a nitrogen stream to produce a prepolymer having a free isocyanate content of 3.36%. Then, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of a urethane prepolymer. Then, 75.3 parts of isophorone diamine, di-n-
To a mixture of 11.8 parts of butylamine, 1221 parts of methyl ethyl ketone and 1018 parts of isopropyl alcohol was added 2037 parts of the urethane prepolymer solution, and then the mixture was mixed at 50 ° C. for 3 days.
Reacted for hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution E) has a resin solid content concentration of 30.
%, The viscosity was 1800 cP / 25 ° C. The number average molecular weight of the polyurethane resin was 29,000.

Production Example 13 The polyester polyol 1000 obtained in Production Example 6 was placed in a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube.
Parts and m-tetramethylxylylene diisocyanate 203
After preparing a prepolymer having a free isocyanate content of 3.37% by reacting it in a nitrogen stream at 130 ° C. for 6 hours, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of the urethane prepolymer. Then isophorone diamine
To the mixture consisting of 76.5 parts, di-n-butylamine 8.3 parts, methyl ethyl ketone 1188 parts and isopropyl alcohol 1002 parts, was added the urethane prepolymer solution 2018 parts,
Then, the mixture was reacted at 50 ° C for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution F) had a resin solid content concentration of 30% and a viscosity of 1100 cP / 25 ° C. The number average molecular weight of the polyurethane resin was 38,000.

Production Example 14 The polyester polyol 1000 obtained in Production Example 7 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
And 333 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to produce a prepolymer having a free isocyanate content of 3.00%. Then, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of the urethane prepolymer. Then, isophoronediamine 74.9 parts, di-n-
2148 parts of the urethane prepolymer solution was added to a mixture consisting of 9.1 parts of butylamine, 1389 parts of methyl ethyl ketone and 1102 parts of isopropyl alcohol, and then added at 50 ° C. for 3 hours.
Reacted for hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution G) has a resin solid content concentration of 30.
%, The viscosity was 1400 cP / 25 ° C. The number average molecular weight of the polyurethane resin was 40,000.

Examples 1 to 4 and Comparative Examples 1 to 4 Titanium white (rutile type) 30 parts Polyurethane resin solution obtained in Production Examples 8 to 14 50 parts Toluene 10 parts Isopropyl alcohol 10 parts A mixture of compositions was respectively applied with a paint shaker. A white printing ink was prepared by kneading. Obtained mixture 10
35 parts of toluene and 15 parts of isopropyl alcohol were added to 0 part to adjust the viscosity to prepare a white printing ink of 9 points as shown in Table 1. The white printing ink of Comparative Example 4 is a two-pack type printing ink obtained by further adding 2 parts of isophorone diisocyanate to those obtained in Comparative Example 1.

The 10 white printing inks obtained were applied with a simple gravure printing machine equipped with a gravure plate with a plate depth of 30 μm to a thickness of 15 μm.
m corona discharge treated nylon film (NY) discharge treated surface and 11 μm thick polyethylene terephthalate (PET)
Was printed on one side and dried at 40 to 50 ° C. to obtain a printed film.

Then, the solid content of 25% on the printing surface of the obtained printing film
A polyurethane adhesive of (3) was applied and dried at a coating amount of 3 g / m ² , and then a 60 μm polyethylene film was dry laminated with a laminator to obtain a laminated film.
The laminate strength (adhesive strength) and the suitability for boiling at 100 ° C. of the thus obtained laminate film were evaluated. The evaluation results are shown in Table 1.

Boilability (1) Evaluation by change in appearance of film Laminated film was observed for change in appearance after boiling at 100 ° C for 30 minutes.

○: There is nothing wrong with the film.

△: Is a small part of the film delaminated?
Or there are few blister but they are occurring.

×: A part of the film is delaminated or blisters occur.

(2) Change due to laminating strength (adhesive strength) 15m after laminating the laminated film at 100 ℃ for 30 minutes
T-type peel strength (unit: g / 15 mm) was measured with a peel tester at a speed of 300 mm / min and compared with the strength before boil.

Production Example 15 1000 parts of long-chain dibasic acid (trade name IPS-22, Okamura Oil Co., Ltd.) and 2-ethylhexylglycidyl were placed in a round-bottomed flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas inlet tube. Esterification was carried out for 20 hours while charging 650 parts of ether and removing condensed water at 200 ° C. under a nitrogen stream. After confirming that the acid value of the polyester became 2 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, hydroxyl value 53KOHmg / g, acid value 0.3KOHmg / g, number average molecular weight 200
1460 parts of 0 polyester polyol were obtained.

Production Example 16 The polyester polyol obtained in Production Example 15 was placed in a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube.
00 parts and 222 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to produce a prepolymer having a free isocyanate content of 3.36%. Then, 815 parts of methyl ethyl ketone was added to obtain a uniform solution of urethane prepolymer. Then, 2037 parts of the urethane prepolymer solution was added to a mixture of 77.5 parts of isophoronediamine, 8.4 parts of di-n-butylamine, 1220 parts of methyl ethyl ketone and 1017 parts of isopropyl alcohol, and then reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution H) has a resin solid content concentration of 30%,
The viscosity was 420 cP / 25 ° C. The number average molecular weight of the polyurethane resin was 39,000.

Example 5 Titanium white (rutile type) 30 parts Polyurethane resin solution obtained in Preparation Example 50 50 parts Toluene 10 parts Isopropyl alcohol 10 parts A mixture of compositions was kneaded with a paint shaker to prepare a white printing ink. . Obtained mixture 10
To 0 parts of the solution, 35 parts of toluene and 15 parts of isopropyl alcohol were added to adjust the viscosity to prepare a two-point white printing ink as shown in Table 2. The two white printing inks obtained were evaluated in the same manner as in Examples 1 to 4. The evaluation results are shown in Table 2.

EFFECTS OF THE INVENTION A one-pack type printing ink using the binder for a printing ink of the present invention has excellent adhesiveness and boil resistance to various plastic films such as polyester, nylon film, polyethylene and polypropylene which are print targets. Has the effect of presenting.

Claims (1)

[Claims] 1. A dibasic acid having 20 to 28 carbon atoms is at least 50.
A polyester diol consisting of a dibasic acid component and a glycol component contained in a weight percentage and having a number average molecular weight of 500 to 4000, a diisocyanate compound, and a polyurethane resin obtained by reacting a polyamine as a chain extender. Binder for printing ink.