WO2003018698A1

WO2003018698A1 - Binder for printing ink and printing ink composition containing the same

Info

Publication number: WO2003018698A1
Application number: PCT/JP2002/008708
Authority: WO
Inventors: Hideyuki Kishi; Takuya Miho
Original assignee: Daicel Chemical Industries, Ltd.
Priority date: 2001-08-31
Filing date: 2002-08-29
Publication date: 2003-03-06
Also published as: CN1473181A; JP2003073601A; KR20040028728A

Abstract

A printing ink binder which has excellent adhesion to films of various plastics such as polyesters, nylons, and polyolefins as ink-receiving matters and is suitable especially for printing inks based on a nonaromatic solvent; and a printing ink composition containing the printing ink binder. The printing ink binder comprises a polyurethane containing at least 50 wt.% high-molecular diol which is a polyester diol obtained from a 2,2-dialkyl-1,3-propanediol (A), a dibasic acid ingredient (B), and a lactone (C).

Description

Description: Binder for printing ink and printing ink composition containing the same

The present invention relates to a printing ink binder and a printing ink composition containing the same. Background art

In recent years, with the diversification of packaging materials and the advancement of packaging technology, various plastic films have been developed as packaging materials, and those suitable for packaging materials have been selected and used as appropriate. I have. 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. Printing ink for such printing has an adhesive property to these various plastic films. High performance such as good performance is required.

Conventionally, polyurethane is often used as a binder for printing ink used in such printing ink. In general, printing inks using polyurethane as a binder have excellent adhesion to polyester films and nylon films alone.Adhesion to films is inadequate. To compensate for this, toluene-based printing inks have been used in which chlorinated polypropylene resins are blended with polyurethane.

However, recently, there has been a growing demand for environmentally friendly inks, and the use of aromatic solvents such as toluene in printing inks has been reduced, and inks that do not use aromatic solvents such as toluene have been used. Is required. In low-concentration aromatic solvent-based or non-aromatic solvent-based printing inks (generally referred to as non-toluene-based printing inks), non-aromatic solvents such as methylethyl ketone and ethyl acetate are mainly used as solvents. The chlorinated polypropylene resin is difficult to dissolve in the ink There was a problem that sufficient adhesiveness to lum could not be obtained. The emergence of a print ink that solves these problems is eagerly awaited.

Japanese Patent Application Laid-Open No. 9-33885 discloses a molecular weight of 500 to 3,3,5-trimethyl-1,6-hexanediol or 3,5,5-trimethyl-1,6-hexanediol. Polypropylene, polyester and polyamide foil as printing materials containing, as a binder, a polyurethane resin obtained by reacting a polymer polyol containing 50,000 or more polyester glycols at 50% by weight or more with a diisocyanate compound. The invention relates to a composition for printing ink having excellent adhesion to any film of ILM.

Japanese Unexamined Patent Publication No. 522223/1993 discloses a binder for a printing ink mainly containing a polyurethane obtained by reacting a polymer diol, a diisocyanate compound and a chain extender, as a component of the polyurethane. The invention describes a binder for printing inks using 1,2-ethyl-12-alkyl-1,3-propanediol. JP-A-2000-26782 discloses a binder for a printing ink mainly containing a polyurethane obtained by reacting a polymer diol, a diisocyanate compound and an amine chain extender. It describes a binder for printing ink containing 2,4-dialkyl-1,5-pentyldiol as a component of the polymer diol, and a printing ink composition containing the binder.

In addition, Japanese Patent Publication No. 1-162848 discloses that when an organic diisocyanate is reacted with a compound having two or more active hydrogens in a molecule to produce a polyurethane, the above-mentioned compound having active hydrogen is used. An average molecular weight of 500 to 50,000, obtained by an ester exchange reaction between a polyester polyol synthesized by a dehydration esterification reaction of neopentyldaricol and adipic acid and ε-force prolactone, A process for producing a polyurethane having excellent elastic recovery using a polyprolactone polyester polyol having a prolactone content of 40 to 95% by weight is described.

SUMMARY OF THE INVENTION The present invention solves the above-described problems, and has excellent adhesiveness to various plastic films such as polyester, nylon, and polyolefin as a printing substrate, and is particularly suitable for a non-aromatic solvent-based printing ink. An object of the present invention is to provide a printing ink composition comprising a binder for printing and the binder for printing ink. The present inventors have conducted intensive studies to provide a printing ink composition that can solve the above-mentioned problems, and as a result, used a polyurethane resin containing a specific diol as a component as a binder for printing ink. In such a case, they have found that such a problem can be solved, and have completed the present invention. Disclosure of the invention

That is, the present invention relates to a polymer diol, a diisocyanate compound and an amine-based chain extender, wherein the polymer diol comprises 2,2-dialkyl-1,3-propanediol (A), a dibasic acid component (B) and a lactone. The present invention provides a binder for printing ink containing 50% by weight or more of a polyester diol comprising the compound (C).

In the above invention, there is provided a binder for printing ink, wherein the polyester diol contains 5 to 80% by weight of a lactone (C). Further, the present invention provides the binder for printing ink of the above invention, wherein the number average molecular weight of the polyester diol is from 500 to 50,000. Further, the binder for a printing ink according to the invention, wherein the polyurethane has a number average molecular weight of 5,000 to 100,000, and the binder for a non-aromatic solvent type printing ink according to the invention. Provided are a binder for printing ink, a printing ink composition containing the binder for printing ink of the invention, and a printing ink composition of the invention using a non-aromatic solvent. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The binder for a printing ink of the present invention contains, as a main component, a polyurethane obtained by reacting a polymer diol, a diisocyanate compound, and an amine-based chain extender.

As a component of the high molecular weight diol, 50% by weight of a polyesterdiol composed of 2,2-dialkyl-1,3-propanediol (A), a dibasic acid component (B) and a lactone (C) was used. % Or more. This polyester diol is prepared by various known methods. It can be obtained by condensation.

2,2-Dialkyl-1,3-propanediol (A), which is one of the constituent components of the polyester diol (hereinafter sometimes abbreviated as "diol") used in the present invention.

(Hereinafter, it may be abbreviated as "propanediol (A;)".) As long as it is a 1,3-propanediol derivative having an alkyl group having 1 to 5 carbon atoms. Specifically, 2,2-getyl-1,3-propanediol, 2_n-butyl-2-ethyl_1,3-propanediol and the like are preferably used. It is desirable to use propanediol (A) alone, but when propanediol (A) is the main component, various other known diols can be used in combination. For example, ethylene glycol, jeti-lendaricol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyldaricol, 2-methyl-1,3-propanediol, 3-methyl-1 , 5-pentendiol, 1,8-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol and the like. These diols may be contained in a range of 40% by weight or less of the polyester diol.

Further, in the present invention, in addition to the above-mentioned propanediol (A), alkyldaricidyl ethers such as n-butyldaricidyl ether, 2-ethylhexyldaricidyl ether, and monocarboxylic acids such as versatic acid glycidyl ester Glycidyl esters can also be used in an amount of up to 40% by weight of the polyester diol.

Dibasic acid component which is one of the constituent components of the polyester diol used in the present invention

As (B), those generally known as an acid component of a polyester as described below can be used. For example, dibasic acids such as adipic acid, maleic acid, fumaric acid, fumaric anhydride, isophthalic acid, terephthalic acid, succinic acid, malonic acid, daltaric acid, azelaic acid, sebacic acid, suberic acid, etc. Acid anhydride and dimeric acid. Of these, adipic acid, azelaic acid and the like are preferably used.

The lactones (C) which are one of the components of the polyester diol used in the present invention include aptyrolactone, ε-force prolactone, <5-valerolactone, monomethyl-ε-force prolactone, and trimethyl-ε. Methylation of one-stroke prolactone ε —Force prolactone and the like. Of these, ε-force prolactone is preferred. The content of the lactone (C) constituting the polyester diol of the present invention is preferably from 5 to 80% by weight of the polyester diol, and more preferably from 10 to 70% by weight. When the content of the lactone (C) is 5% by weight or less, the adhesive strength and the blocking resistance may decrease. On the other hand, when the content is 80% by weight or more, the printability tends to deteriorate due to the decrease in solubility.

The number average molecular weight of the polyester diol of the present invention comprising a diol containing 2,2-dialkyl-11,3-propanediol (ジ), a dibasic acid component (Β) and a lactone (C) is as follows: It is appropriately determined in consideration of the solubility, drying property, blocking resistance, and the like of the obtained polyurethane, and preferably has a lower limit of 500, more preferably 700, and an upper limit of 500, more preferably 4. A value within the range of 0 0 0 is preferred. If the number average molecular weight is less than 50,000, printability tends to be inferior due to the decrease in solubility, while if it exceeds 50,000, drying properties and blocking resistance tend to decrease.

The method for producing the polyester diol is as follows: 2,2-dialkyl-1,3-propanediol (A) η + 1 mol, diacid component (Β) η mol, lactones (C) 5 to 80% by weight % Can be produced, for example, according to the method described in JP-A-58-59212.

That is, the diol (Α), the dibasic acid component (Β), and the lactone (C), for example, ε-force prolactone, are mixed and heated, and can be produced by a dehydration esterification reaction, a ring opening reaction, and a transesterification reaction. (One-pot method) or polyester diol obtained by dehydration esterification of diol (Α) and dibasic acid component (Β), and separately from polyhydric alcohol by ring-opening reaction of ε-force prolactone. It can also be produced by mixing a polyprolactone polyol, usually a polyprolactonediol, and then transesterifying the two. Further, it can be produced by ring-opening polymerization of ε-force prolactone to a polyester polyol having a small molecular weight. Of these, the one-pot method is simple and preferred.

These reactions are preferably performed at 130 to 240 :, preferably 140 to 230, from the viewpoint of preventing coloring and from the viewpoint of preventing the depolymerization reaction of ε-force prolactone. . For these reactions, the catalyst is usually added at 0.05 to 100 ppm by weight of the total monomer, Preferably, 0.1 to 100 ppm by weight is used. Examples of the catalyst include organotitanium compounds such as tetrabutyl titanate and tetrapropyl titanate, dibutyltin laurate, tin octoate, dibutyltin oxide, stannous chloride, stannous bromide, and tin tin iodide. Tin compounds can be used. The reaction is preferably carried out while passing an inert gas such as nitrogen from the viewpoint of preventing the obtained target product from being colored.

Further, a low molecular weight diol having a number average molecular weight of less than 500 may be used in combination as long as the performance of the polyurethane of the present invention is not deviated. Specific examples include 2,2-dialkyl-1,3-propanediol described in the section of the diol used in the polyester diol of the present invention and various other diols. The amount of the low molecular weight diol is usually less than 10 parts by weight based on 100 parts by weight of the high molecular weight diol. If the amount is more than 10 parts by weight, the printability tends to decrease due to the decrease in solubility, and the adhesiveness to the nylon film tends to decrease.

In the present invention, various known diisocyanates of an aromatic, aliphatic or alicyclic type can be used as the diisocyanate compound. For example, 1,5-naphthylenediocyanate, 4,4'-diphenylmethanediisocyanate, 4,4'-diphenyldiphenylmethanediisocyanate, tetraalkyldiphenylmethyldiisocyanate, 1,3_phenylene 1,4-diene diisocyanate, 1,4-phenylene diisocyanate, 1,4-diisocyanate, butane-1,4-diisocyanate, hexanemethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4 diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4 , 4-diisocyanate, 1,3-bis (isocyanatemethyl) cyclo Hexane, methylcyclohexanediisocyanate, m-tetramethylxylylenediisocyanate, and dimer diisocyanate obtained by converting a carboxy group of dimer acid into an isocyanate group are mentioned as typical examples.

In the present invention, an amine-based chain extender is used particularly in consideration of adhesiveness to a nylon film. As the amine-based chain extender, specifically, aromatic, aliphatic or alicyclic Examples of various known diamines include phenylenediamine, naphthylenediamine, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-14,4′-diamine, and the like. In addition, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine Examples of amine-based chain extenders include diamines having a hydroxyl group in the molecule, such as diamine, di-2-hydroxypropylethylenediamine, and dimer diamine obtained by converting a carboxy group of dimer acid into an amino group.

In the present invention, a chain length terminator may be used as necessary. Examples of the chain terminator include various known compounds such as amine-based and lower alcohol-based ones, and amine-based chain terminators are preferred because they can easily control the molecular weight. Examples of the amine-based chain terminator include alkyl monoamines such as di-n-butylamine and hydroxyl monoamines such as genolenoamine. Examples of the lower alcohol-based chain terminator include methanol and ethanol.

The method for producing the polyurethane used in the present invention is not particularly limited.For example, a polymer diol and a diisocyanate compound are reacted under the condition of an excess of isocyanate group, and a prepolymer having an isocyanate group at both terminals of the polymer diol is used. (Preferably 0.5-10% isocyanate group content) and then reacting it with an amine-based chain extender and, if necessary, a chain-terminating agent in a suitable solvent, In addition, any one-step method in which a high molecular diol, a diisocyanate compound, an amine-based chain extender and, if necessary, a chain terminator are reacted in a suitable solvent at once can be employed, but a uniform polymer solution can be used. It is preferable to employ the two-stage method in that it is easy to obtain. In the production of these polyurethanes, various known catalysts such as tin catalysts such as stannous octoate can be added.

When the polyurethane used in the present invention is produced by a two-step method, the conditions for reacting the high molecular weight diol with the diisocyanate compound are not particularly limited, except that the isocyanate group is excessive, but the hydroxyl group isocyanate group is not required. Is preferably in the range of 1.5 to 13.5 in equivalent ratio. In producing the printing ink binder of the present invention, the solvent used is generally an aromatic solvent such as benzene, toluene, or xylene which is well known as a printing ink solvent; methanol, ethanol, isopropanol, or the like. alcohol solvents such as n-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; these may be used alone or in combination of two or more. Can be used as a mixture. When a non-aromatic solvent-type printing ink is obtained using the printing ink binder of the present invention, it is preferable to use a non-aromatic solvent also in producing the printing ink binder.

The number average molecular weight of the polyurethane used in the present invention obtained in this manner is preferably in the range of 50,000 to 100,000, more preferably in the range of 500,000 or less. Is good. When the number average molecular weight is less than 5,000, the drying properties, blocking resistance, film strength, oil resistance, etc. of the printing ink using this as a vehicle are liable to decrease. When it exceeds 000, the viscosity of the printing ink binder, which is the polyurethane resin solution, increases, and the gloss of the printing ink tends to decrease. Further, the resin solid content concentration 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 1%. It is practically preferable to adjust the value to the range of 0, 000 cP / 25.

Further, in the binder for printing ink of the present invention, if necessary, the following resin may be used as a binder as an auxiliary component in addition to the polyurethane which is a main component of the present invention. For example, polyurethanes, polyamides, dinitrocellulose, polyacrylic esters, polypinyl chlorides, copolymers of vinyl chloride and vinyl acetate, rosin resins, ketone resins, etc., other than the present invention are mentioned.

A color mill, a solvent, and, if necessary, a surfactant, a wax, and other additives for improving the ink fluidity and the ink surface film are appropriately blended with the binder for the printing ink of the present invention, and a pole mill, an attritor, and a sand mill are used. The printing ink composition of the present invention can be manufactured by kneading using an ordinary ink manufacturing apparatus such as the above. As the solvent, those similar to those described in the production of the binder for printing ink can be used. When the printing ink composition of the present invention is used as a non-aromatic solvent-type printing ink, a non-aromatic solvent is used during production of the printing ink binder, and A non-aromatic solvent is also used when producing a printing ink composition. The amount of the binder in the printing ink composition is preferably such that the resin solid content is 3 to 20% by weight. Example

Hereinafter, the present invention will be further described with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, parts and% indicate parts by weight and% by weight, respectively.

(Synthesis example 1)

In a four-necked flask equipped with a stirrer, thermometer and nitrogen gas inlet tube, 346 parts of adipic acid, 539 parts of 2-n_butyl_2-ethyl-1,3_propanediol, and 200 parts of ε-force prolactone And 0.04 part of a tetrabutyl titanate catalyst, and the mixture was kept at a temperature of 220 in a nitrogen atmosphere and reacted for 18 hours while being dehydrated. Polyesterdiol with a lactone content of 60% was obtained with a value of 55.2 Hmg / g and an acid value of 0.11 KOHmgZg.

(Synthesis example 2)

Using the same reactor as in Synthesis Example 1, 237 parts of adipic acid and 1 part of 2-n_butyl_2-ethyl-1,3-propanediol 42, 1400 parts of ε-force prolactone, and tetrabutyl titanate 0 .04 parts were charged, and kept at a temperature of 220 under a nitrogen atmosphere, and reacted for 15 hours while removing water. A polyester diol having an OH value of 55.2 KOH mg / g and an acid value of 0.12 KOH mgZg and a lactone content of 70% was obtained.

(Synthesis example 3)

Using the same reactor as in Synthesis Example 1, 454 parts of adipic acid, 658 parts of 2-n_butyl_2-ethyl-1,3-propanediol, 1000 parts of ε-force prolactone and 1,000 parts of tetrabutyl thiocyanate. 04 parts were charged, and kept at a temperature of 220 under a nitrogen atmosphere, and reacted for 22 hours while dewatering. Was obtained 〇_H number 55. 9KOHmg / g _¾ acid value 0. 10 KOH lactone content of 50% polyester diol MgZg.

(Synthesis example 4)

Using the same reactor as in Synthesis Example 1, 454 parts of adipic acid, 658 parts of 2,4-getyl-1,5-pentynediol, 1,000 parts of ε-force prolactone and 1,000 parts of tetrabutyltin After adding 0.04 parts of the evening salt, the mixture was kept at a temperature of 220 under a nitrogen atmosphere and reacted for 23 hours while dehydrating. A polyester diol having an OH value of 55.6 K〇Hmg / g and an acid value of 0.05 KOHmg g and a lactone content of 50% was obtained.

(Synthesis example 5)

Using the same reactor as in Synthesis Example 1, 628 parts of sebacic acid, 484 parts of 3-methyl-1,5-diaminediol, 1000 parts of ε-force prolactone and 0.04 part of tetrabutylthiocyanate were charged. The reaction was maintained at a temperature of 220 under a nitrogen atmosphere and reacted for 24 hours while dehydrating. A polyester diol having an OH value of 55.4 K〇Hmg / g and an acid value of 0.08 KOH mg / g and a lactone content of 50% was obtained.

(Synthesis example 6)

Using the same reactor as in Synthesis Example 1, 995 parts of adipic acid, 1250 parts of 2-n-butyl-2_ethyl-1,3-propanediol and 0.04 part of tetrabutylethyl nitrate were charged, and the temperature was 220 in a nitrogen atmosphere. The reaction was carried out for 26 hours while dehydrating. Polyesterdiol with a 〇1 ^ value of 58. OKOHmgZg and an acid value of 0.20 KOHmg / g was obtained.

[Example 1]

In a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 325 parts of the 60% lactone-containing polyesterdiol obtained in Synthesis Example 1 and 54.9 parts of isophorone diisocyanate were charged. After reacting at 120 ° C for 6 hours under a nitrogen stream to produce a prepolymer, 573 parts of methylethylketone was added to obtain 953 parts of a homogeneous urethane prepolymer solution. Next, a mixture consisting of 12.92 parts of isophorone diamine, 0.49 parts of monoethanolamine and 345 parts of isopropyl alcohol was added to the urethane prepolymer solution, and reacted at 50 for 3 hours. The polyurethane resin solution A thus obtained had a resin solid content concentration of 30.2% and a viscosity of 826 cp / 25:

[Example 2]

Using the same reactor as in Example 1, 325 parts of the poly (ester diol) having a lactone content of 70% obtained in Synthesis Example 2 and 54.9 parts of isophorone diisocyanate were charged, and the mixture was stirred at 120 with nitrogen in a stream of nitrogen. After reacting for a time to produce a prepolymer, 574 parts of methylethyl ketone was added to obtain 954 parts of a homogeneous solution of urethane prepolymer. Then iso A mixture consisting of 12.9 parts of holondiamine, 0.48 parts of monoethanolamine and 345 parts of isopropyl alcohol was added and reacted at 50 for 3 hours. The polyurethane resin solution B thus obtained had a resin solids concentration of 30.2% and a viscosity of 1992 cp / 25.

[Example 3]

Using the same reactor as in Example 1, 1 part of the polyester diol having a lactone content of 50% obtained in Synthesis Example 3 and 34.9 parts of isophorone diisocyanate were charged, and the mixture was reacted under a nitrogen stream at 120. After reacting for 6 hours to produce a prepolymer, 568 parts of methylethyl ketone was added to obtain 943 parts of a homogeneous solution of urethane prepolymer. A mixture consisting of 12.92 parts of isophorone diamine, 0.49 parts of monoethanolamine, and 341 parts of isopropyl alcohol was added, and the mixture was reacted at 50 for 3 hours. The polyurethane resin solution C thus obtained had a resin solid content concentration of 30.8% and a viscosity of 1175 cp / 25.

[Comparative Example 1]

Using the same reaction apparatus as in Example 1, Kurapole P2010 (polyester polyol of adipic acid having an average molecular weight of 2000 and 3-methylpentanediol, OH value 57.1) manufactured by Kuraray Co., Ltd. Parts and isophorone diisocyanate (54.9 parts) were charged and reacted with 12 O for 6 hours under a nitrogen stream to produce a prepolymer, and then 558 parts of methyl ethyl ketone were added to obtain 927 parts of a homogeneous urethane prepolymer solution. Was. A mixture consisting of 12.93 parts of isophorodiamine, 0.5 part of monoethanolamine, and 335 parts of isopropyl alcohol was added, and the mixture was reacted at 50 for 3 hours. The polyurethane resin solution D thus obtained had a resin solid content concentration of 30.1% and a viscosity of 2048 cp / 25.

[Comparative Example 2]

Using the same reaction apparatus as in Example 1, 323 parts of a 50% lactone-containing polyesterdiol obtained in Synthesis Example 4 and 54.9 parts of isophorone diisocyanate were charged, and the mixture was stirred at 120 ° C under a nitrogen stream. After reacting for 6 hours to produce a prepolymer, 570 parts of methyl ethyl ketone was added to obtain 947 parts of a homogeneous solution of urethane prepolymer. Isophorone diamine 12.9 parts, monoethanolamine 0.47 parts and isopropyl alcohol A mixture of 342 parts was added and then reacted at 50 for 3 hours. The polyurethane resin solution E thus obtained had a resin solid content concentration of 30.7% and a viscosity of 1843 cp / 25X :.

[Comparative Example 3]

Using the same reaction apparatus as in Example 1, 324 parts of the polyesterdiol having a lactone content of 50% obtained in Synthesis Example 5 and 4.9 parts of isophorone diisocyanate were charged, and the mixture was placed under a nitrogen stream. The mixture was reacted at 120 for 6 hours to produce a prepolymer, and 572 parts of methylethyl ketone was added to obtain 950 parts of a homogeneous solution of a urethane prepolymer. A mixture consisting of 12.9 parts of isophorone diamine, 0.47 parts of monoethanolamine and 343 parts of isopropyl alcohol was added, followed by reaction at 50 for 3 hours. The polyurethane resin solution F thus obtained had a resin solids concentration of 30.4% and a viscosity of 8786 cp / 25.

[Comparative Example 4]

Using the same reaction apparatus as in Example 1, 310 parts of the polyester diol obtained in Synthesis Example 6 and 54.9 parts of isophorone diisocyanate were charged and reacted at 120 under a nitrogen stream for 6 hours. After the prepolymer was manufactured, 551 parts of methyl ethyl ketone was added to obtain 916 parts of a homogeneous solution of urethane prepolymer. A mixture consisting of 12.9 parts of isophorone diamine, 0.49 parts of monoethanolamine and 331 parts of isopropyl alcohol was added, followed by reaction at 5 for 3 hours. The polyurethane resin solution G thus obtained had a resin solids concentration of 29.4% and a viscosity of 1500 cp / 25. The following evaluations were performed using the polyurethane resins A to G obtained in Examples 1 to 3 and Comparative Examples 1 to 4. The results are shown in Table 1.

To 100 parts of the polyurethane resin, 90 parts of titanium white (rutile type) 90 parts of methylethyl ketone, 40 parts of ethyl acetate, and 30 parts of isopropyl alcohol were kneaded with a paint shaker. The obtained white printing ink is applied to a glass plate with Barco overnight (100 m), left at room temperature (about 25) for 30 seconds, and then methyl ethyl ketone isopropyl alcohol Z ethyl acetate is applied. It was immersed in a solvent with a weight ratio of 1: 1: 1, and the time required for the ink to melt and flow was measured. Adhesive test · Peeling off>

The obtained polyurethane resin solution (without ink formulation) is applied to one side of various plastic films using Barco No. 1 (No. 4), air-dried (about 25), and then dried at 80 for 1 hour. After drying, the film was folded inward, a glass plate was placed thereon, and the film was further dried at 80 at 1 hour to obtain a laminated film. Then, after the laminate film was formed into a strip having a width of 25 mm, the peel strength was determined by a tensile tester. Table

OP P film: 50 m thickness, use for surface treatment side

PET film: 50 m thickness

NY (6-nylon) film: 15 zm thick, use on the surface treated side, industrial use by Mitsubishi MFG

The binder for printing ink of the present invention and the printing ink composition containing the same can be used for various plastic films such as polyester, nylon film, polyethylene, polypropylene and the like, even when a non-aromatic solvent-based printing ink is used. And exhibits excellent adhesiveness. Further, as compared with the case where another similar polyester diol is used as the polymer diol in place of the polyester diol of the present invention, the binder for printing ink and the printing ink composition of the present invention have a non-aromatic solvent type. Print Re-dissolvability is good. For this reason, the binder for printing ink and the printing ink composition of the present invention are to be replaced with a binder and a printing ink composition for toluene-type printing ink in which a chlorinated polypropylene resin is blended with a conventional polyurethane. It is also preferable in terms of environmental impact.

Claims

The scope of the claims

1. A high-molecular diol, a diisocyanate compound and an amine-based chain extender are reacted, and the high-molecular diol is composed of 2,2-dialkyl-1,3-propanediol (A), a dibasic acid component (B), and a lactone. A binder for printing ink, comprising at least 50% by weight of a polyester diol comprising (C).

2. The binder for printing ink according to claim 1, wherein the polyester diol contains 5 to 80% by weight of a lactone (C).

3. The binder for printing ink according to claim 1, wherein the number average molecular weight of the polyester diol is from 500 to 5,000.

4. The binder for a printing ink according to any one of claims 1 to 3, wherein the number average molecular weight of the polyurethane is from 5,000 to 100,000.

5. The binder for printing ink according to any one of claims 1 to 4, which is a non-aromatic solvent-type binder for printing ink.

6. A printing ink composition comprising the printing ink binder according to claim 1.

7. The printing ink composition according to claim 6, wherein a non-aromatic solvent is used.