WO2005040293A1 - Printing ink binder and printing ink composition - Google Patents

Abstract

A printing ink binder that is suitable as a non-toluene printing ink binder making no use of toluene or has an aptitude of direct laminating not using any organic solvents; and a printing ink composition comprising the printing ink binder.

Description

 Description Binder for printing ink and printing ink composition

 The present invention relates to a binder for printing ink comprising a polyurethane resin and a printing ink composition containing the same. More specifically, a low-toxic organic solvent such as ethyl acetate or isopropyl alcohol is used, that is, it does not use toluene.It is suitable for non-toluene type binders for printing inks, or it does not use organic solvents. The present invention relates to a binder for printing ink, and a printing ink composition using the same. Background art

 Conventionally, in the manufacture of packaging materials called flexible packages based on plastic films such as polyester (PET) film, nylon (NY) film, and stretched polypropylene (OPP) film, gravure printing is applied to the film substrate. Or, after printing by flexo printing or the like, polyethylene film or unstretched polypropylene film is usually laminated by dry lamination or extrusion lamination for the purpose of heat sealing, airtightness, decoration or surface protection. Done.

With the development of packaging technology, the functions required for printing ink binders used in printing inks are also diversifying. Not only are they suitable for printing, but they are also suitable for adhesion to a wide range of substrates, heat resistance, and retort resistance. Resistance, boil sterilization resistance, weather resistance, etc. are required, and from environmental issues to biodegradability. Conventionally, polyurethane resins have been widely used as binders for printing inks, but no binders for printing inks satisfying these functions widely have yet been obtained. In the past, organic solvent-based printing inks have become widespread, and as the binder resin, polyurethane resins that have a wide range of adhesion to films using various substrates such as PET, NY, and PP are generally used. It is used, but its adhesion to general-purpose films such as polyethylene film and polypropylene film is insufficient. Therefore, for the purpose of improving the adhesive strength to a polyethylene film or a polypropylene film, for example, as shown in Japanese Patent Application Laid-Open No. H10-72562 and Patent Publication No. Polyurethane resin containing a polyol as a main component is used. However, printing inks containing polyurethane resins obtained using these polyols have excellent adhesion to polyolefin-based substrates, but are subjected to boil sterilization, retort sterilization, etc. after packaging the food. If a one-pack ink containing a polyurethane resin is used to print a plastic film used as a packaging substrate, the printed packaging substrate will have boil and retort resistance (hereinafter, collectively). (Boil resistance etc.). In addition, a binder for a printing ink made of a polyurethane resin made of a lactone polyol obtained by ring-opening polymerization of ε-force prolactone is excellent in boil resistance, etc. and weather resistance. There were problems with solubility in water and printability.

In fields requiring boil resistance and retort resistance, etc., one-pack inks are difficult to use, and despite these disadvantages, two-pack reactive inks still containing a polyisocyanate compound are still mainstream. It is the current situation. The present invention solves the above-described problems, and when various plastic films such as polyester, nylon, polyethylene, and polypropylene are used as a packaging base material to be printed, the present invention has excellent adhesiveness to them, and furthermore has excellent resistance. It is an object of the present invention to provide a printing ink binder having retort properties and pore resistance, and a printing ink composition using the same. Disclosure of the invention

 The present inventors have conducted intensive studies to provide a one-pack type printing ink binder that can solve the above-described problems, and as a result, used a polyurethane resin containing a specific polyol as a constituent component as a printing ink binder. In such a case, they have found that the above-mentioned problem can be solved, and have completed the present invention.

 That is, a first aspect of the present invention relates to a printing ink binder containing, as a main component, a polyurethane resin (D) obtained by reacting a polyol component (A), an isocyanate compound (B), and a chain extender (C). The polyol component (A) is a ring-opening copolymer of ε-force prolactone and δ-valerolactone in a molar ratio of 20/80 to 80/20 using a polyol compound having at least two active hydrogen groups as an initiator. A binder for printing ink, comprising a copolymerized lactone polyol (a1) having a number average molecular weight of 400 to 20,000 and wherein (al) accounts for at least 40% by weight of the polyol component (A). provide. A second aspect of the present invention provides the binder for printing ink according to the first aspect of the present invention, wherein the chain extender (C) is a polyol compound or a polyamine compound having at least two active hydrogen groups. . Furthermore, a third aspect of the present invention provides a printing ink composition containing the binder for printing ink according to the first or second aspect of the present invention. In addition, a fourth aspect of the present invention provides the printing ink composition according to the third aspect of the present invention, which is a one-pack type. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described.

 In the present invention, the copolymerized lactone polyol (al) is a ring-opening copolymer of ε-force prolactone and δ-palerolactone using at least one polyol compound having at least two active hydrogen groups as an initiator. A copolymerized lactone polyol having a polymerized number average molecular weight of 400 to 20,000;

(al) accounts for at least 40% by weight of the polyol component (A). In order to synthesize the copolymerized lactone polyol (al) used in the present invention, a general method for obtaining a lactone-modified polyol compound by ring-opening polymerization of a cyclic lactone compound can be used. That is, it is obtained by reacting an initiator and a mixture of ε-force prolactone and δ-valerolactone at 120 ° C. to 250 ° C. for 2 to 50 hours in the presence of a catalyst.

The initiator used to synthesize the copolymerized lactone polyol (al) used in the present invention may be any initiator as long as it is a low molecular weight compound having at least two active hydrogen groups in one molecule. Various known components known as glycol components of polyesters can be used. For example, the molecular weight is 100,000 or less, preferably 500, or less, more preferably 200, or less, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,2 3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-propyl-1,3-propanediol, 2, 2, -Jetyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butenediol, dipropylene glycol, etc. Known glycols may be mentioned. In the present invention, in addition to the above-mentioned glycols, alkyldaricidyl ethers such as n-butyldaricidyl ether and 21-ethylhexyldaricidyl ether; Can also be used as a kind of glycols. Further, compounds having three or more active hydrogen groups in one molecule, such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, Sorbitol, Penyu erythri 1 ^ 1 l and the like. Among these polyols, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, 6 Hexanediol, trimethylolpropane and glycerin are particularly preferred.

 The composition ratio of the two types of cyclic lactone compounds used in the present invention, ε-force prolactone and δ-valerolactone, is from 20/80 to 80 820, preferably 40%, by molar ratio (%). / 60 to 60/40. ε-force prolactone and δ-pallet mouth When one component of the lactone compound of the lactone exceeds 80 mol%, the crystallinity of the obtained copolymerized lactone polyol (al) becomes high, and polyurethane is formed. When used as a binder for inks, the solubility in organic solvents deteriorates, which is not preferable. If necessary, ε-force prolactone and (5-valerolactone as well as trimethyl-1-ε-force prolactone, monomethyl-ε-force prolactone, τ-butyrolactone, monomethyl- <5-valerolactone, etc. are added. When a third or subsequent cyclic lactone compound is added, the amount of addition is not more than 20 mol% in 100 mol% of the total cyclic lactone compound.

The number-average molecular weight of the copolymerized lactone polyol (al) used in the present invention is preferably from 400 to 200 in consideration of the solubility of the obtained polyurethane resin (D) in an organic solvent, drying properties, blocking resistance and the like. 0, 0000, and preferably in the range of 1, 0000 to 100, 0000. When the number average molecular weight is less than 400, the solubility of the printing ink binder in an organic solvent tends to decrease, and the printing suitability tends to deteriorate. It becomes too hard and loses flexibility, and its adhesion to various substrates such as polyethylene film and polypropylene film decreases. On the other hand, if it exceeds 200,000, the drying property and the anti-booking property of the printing ink composition containing the binder for printing ink of the present invention containing the polyurethane resin (D) as a main component tend to decrease. Not preferred. The copolymerized lactone polyol (al) used in the present invention may be used alone for the polyurethane resin (D). If it is within the range not to be used, it can be used in combination with other polyols. For example, polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran; polyester polyols obtained by condensing a dibasic acid and a glycol component; and cyclic ester compounds such as lactone compounds Polylactone polyols obtained by ring-opening polymerization of a polyol compound having at least two active hydrogen groups as initiators, other polycarbonate polyols, polybutadiene glycols, and bisphenol A Various known polymer polyols generally used in the production of polyurethane, such as glycols obtained by adding ethylene oxide or propylene oxide, may be mentioned. The copolymerized lactone polyol (al) used in the present invention accounts for at least 40% by weight of the polyol component (A), preferably at least 50% by weight, and particularly preferably at least 60% by weight.

 The proportion of (al) in (A) is less than 40% by weight, and the retort resistance, poiling resistance and weather resistance tend to be poor, which is not preferred. In the present invention, the polyol component (A), the isocyanate compound (B) and the chain extender (C) are reacted to form a polyurethane resin (D), which is used as a binder for printing ink. As), various known aromatic, aliphatic or alicyclic polyisocyanates can be used.

 For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4, diphenyldimethylmethane diisocyanate, 4, to, tetraalkyldiphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1,4 -phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4 Monotrimethylhexamethylene diisocyanate, 2,2,4-trime

-To, cyclohexane-1,4-diisocyane 1, xylylene diisocyanate, isophorone diisocyanate, lysine disocyanate, dicyclohexyl methane 1,4,4-diisocyanate, 1,3-bis (isocyanone methyl) cyclohexane, to methyl mouth Typical examples thereof include xanthocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate obtained by converting a carboxyl group of dimer monoacid into an isocyanate group. Of these, isophorone diisocyanate, hexylene diisocyanate, 4,4, -diphenylmethane diisocyanate, and tolylene diisocyanate are preferred. Examples of the chain extender (C) used in the present invention include, for example, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, dimethylenetriamine, isophoronediamine, dicyclohexylmethane-1,4,4-diamine And the like. In addition, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine Representative examples thereof include diamines having a hydroxyl group in a molecule such as di-2-hydroxypropylethylenediamine, and low molecular weight glycols described in the above-mentioned section of polyester diols and dimer diamines obtained by converting a lipoxyl group of dimer acid into an amino group. As an example.

 Further, if necessary, a chain length terminator or a terminal blocking agent may be used. Examples of such a chain terminator include dialkylamines such as di-n-butylamine, alcohols such as ethanol and isopropyl alcohol, and amino alcohols such as monoethanolamine.

The method for producing the polyurethane resin (D), which is the main component of the printing ink binder of the present invention, is not particularly limited, and may be produced by any one of a one-shot method in which each component is reacted at a time and a multi-step method. May be. The multi-stage method involves reacting in stages For example, a polyol component (A) and an isocyanate compound (B) are reacted under an excess of isocyanate group to prepare a prepolymer having an isocyanate group at both ends of a molecule of the polyol component (A). This is dissolved in a suitable solvent and reacted with a chain extender and, if necessary, a chain terminator. The reaction is usually carried out at a temperature of from 20 to 140 ° C (preferably from 40 to 120 ° C. However, when an amine compound is reacted as a chain extender (C) or the like, the reaction is usually carried out at 10 ° C. It is carried out at a temperature of 0 ° C. or lower, preferably 0 to 80 ° C.

 Further, in order to accelerate the reaction if necessary, a catalyst used in a usual polyurethane-forming reaction, for example, an amine catalyst such as triethylamine, N-ethylmorpholine, and triethylenediamine, dibutyltin dilaurate, dioctyltin diyl perylate, tin octylate For example, a tin-based catalyst and a titanium-based catalyst such as tetrabutyl titanate may be used.

 If necessary, the reaction may be carried out in an organic solvent, and the organic solvent may be added during or after the reaction. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter sometimes referred to as MEK), methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, ethyl sorbate acetate, and n-hexane. , N-heptane, cyclohexane, tetralin, toluene, xylene and other hydrocarbons, dioxane, tetrahide-furan and other ethers, methanol, ethanol, and isopropyl alcohol (hereinafter also referred to as IPA) Alcohols such as n-propyl ether and butanol, amides such as dimethylformamide and dimethylacetamide, and N-methylpyrrolidone can be used. Among these, it is preferable to use relatively low toxicity MEK, ethyl acetate, butyl acetate, and isopropyl alcohol each alone or in combination.

The number average molecular weight of the urethane resin (D), which is the main component of the printing ink binder of the present invention thus obtained, is in the range of 5,000 to 100,000. Is good. When the number average molecular weight is less than 5,000, drying, blocking resistance, skin strength, oil resistance, etc. of the ink coating film formed from the printing ink composition containing the same are reduced. On the other hand, when it exceeds 100,000, the viscosity of the polyurethane resin (D) (binder for printing ink) solution becomes large, and the solubility in an organic solvent becomes poor. In addition, the gloss of the cured coating film formed from the printing ink composition tends to decrease. The solid concentration of the resin in the polyurethane resin (D) solution is not particularly limited, and may be appropriately determined in consideration of workability at the time of printing, and is usually 10 to 80% by weight, preferably 20 to 60% by weight. Viscosity (Brookfield viscometer) is adjusted in the range of 50 to 100,000 cPZ 25 ° C, preferably 100 to 100,000 cP / 25 ° C It is practically preferable to do so. To control the terminal isocyanate group concentration of the polyurethane resin (D) to a value within the above range, the polyol component (A) and the isocyanate compound are used.

When reacting with (B), there is no particular limitation except that the isocyanate group is excessive, but it is necessary to adjust the equivalent ratio of hydroxyl group / isosinate group to be in the range of 0.3 to 0.9. There is. The printing ink composition of the present invention may contain additives such as an antifoaming agent, a preservative, an antifreezing agent, and a pigment as optional components. Examples of the antifoaming agent include silicone-based or alcohol-based antifoaming agents. Examples of the preservative include organic nitrogen sulfur compound-based or organic sulfur halogen compound-based antiseptic. Examples of the antifreezing agent include ethylene. Glycol and propylene glycol.

The pigment is not particularly limited, and ordinary inorganic and organic pigments can be used. If necessary, other additives such as resins for ink binders, solvents and stabilizers, and pigment dispersants may be added. Other resins include polyamide resin, nitrocellulose, acrylic resin, vinyl acetate resin, biel chloride resin, styrene maleic acid copolymer resin, chlorinated polyolefin, epoxy resin and Gin-based resins. Examples of the stabilizer include hindered phenol-based, hydrazine-based, benzophenone-based, benzotriazole-based, oxalic acid anilide-based, and hinderedamine-based stabilizers. Examples of the pigment dispersant include sorbitan fatty acid esters, partial fatty acid esters of polyacrylic acid, alkylamine fatty acid salts, and alkyldiamines.

 The mixing method of each component is not particularly limited, and a surfactant, a wax, and other additives for improving the ink fluidity and the surface film of the ink are appropriately blended as necessary, and a three-roll, a pole mill, a sand grinder mill The printing ink composition of the present invention can be manufactured by kneading using an ordinary ink manufacturing apparatus such as the above. In the printing ink composition, the blending amount of the binder for printing ink of the present invention is preferably such that the resin solid content is 3 to 20% by weight.

 The printing ink composition containing the binder for printing ink of the present invention can be used as a one-pack type composition for printing ink. Example

 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>

In a round-bottomed flask equipped with a stirrer, thermometer, water separator and nitrogen gas inlet tube, ε-caprolactone (Braxel II, manufactured by Daicel Chemical Industries, Ltd.) 595 parts by weight and <5-valerolactone 3 4 6 Parts by weight and 59 parts by weight of 1,6-hexanediol as an initiator were charged, and polymerization was carried out at 180 ° C. for 6 hours under a nitrogen stream. After confirming that the total content of remaining ε-coprolactone and δ-valerolactone was 2% by weight or less with respect to the total reaction mixture, the degree of vacuum was gradually increased by a vacuum pump, and residual Ε-force prolactone and δ-valerolactone were removed. Thus, the hydroxyl value 56.4 KO Hmg / g, the acid value 0.06 KO Hmg Zg, and the moisture content 0. A copolymerized lactone polyol having 005%, a viscosity of 280 OmPas at 25 ° C and a number average molecular weight of 2,000 was obtained.

(Example 1)

 244 g of the copolymerized lactone polyol obtained in Production Example 1 and isophorone diisocyanate 56 were charged into a separable flask of 5001111, and reacted at 80 ° C. for 4 hours under a nitrogen stream to give an isocyanate group concentration of 3.51% by weight. After the production of the polyurethane resin, 200 g of methyl ethyl ketone was added to obtain a uniform solution of the polyurethane resin having a solid content of 60% by weight. The homogeneous solution of the polyurethane resin had an isocyanate group concentration of 2.1% by weight. Next, 300 g of the homogeneous solution of the polyurethane resin was placed in another 500 ml separable flask, and a mixture consisting of 11.4 g of isophoronediamine, 0.22 g of monoethanolamine, 160 g of methylethylketone, and 168 g of isopropyl alcohol was used. Was added to the uniform solution of the polyurethane resin and reacted at 50 ° C. for 3 hours to effect chain extension and end capping of free isophorone diisocyanate. The obtained solution of the printing ink binder had a resin solid content concentration of 30% by weight and a viscosity of 39 OmPa · sZ25 ° C. The number average molecular weight of the polyurethane resin was 39,000, and the isocyanate group concentration was 0.01% by weight or less. Manufacturing example 2>

A round bottom flask similar to that of Production Example 1 was charged with 772 parts by weight of ε-force prolactone, 169 parts by weight of δ-valerolactone, and 118 parts by weight of 1,6-hexanediol as an initiator. At 180 ° C. for 6 hours. After confirming that the total content of remaining ε-force prolactone and δ-valerolactone was 2% by weight or less based on the entire reaction mixture, the degree of vacuum was gradually increased by a vacuum pump, and the remaining Ε-force prolactone and <5-valerolactone were removed. like this A lactone polyol having a hydroxyl value of 56.3K〇Hmg / g, an acid value of 0.2KOHmgZg, a water content of 0.004% by weight, a viscosity at 25 ° C of 2,60 OmPas and a molecular weight of 2,000 was prepared. Obtained.

(Example 2)

 244 g of the copolymerized lactone polyol obtained in Production Example 2, 56 g of isophorone diisocyanate, 12.4 g of isophorone diamine as a chain extender, and 0.22 g of monoethanolamine as a terminal sealant. Except for the above, a polyurethane resin solution as a binder for printing ink was obtained in the same manner as in Example 1. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 3,100 mPa · s / 25 ° C. The polyurethane resin had a number average molecular weight of 46,500 and an isocyanate group concentration of 0.01% by weight or less.

<Production Example 3>

 In a round-bottom flask similar to that of Production Example 1, 209 parts by weight of ε-force prolactone, 732 parts by weight of δ-valerolactone, and 59 parts by weight of 1,6-hexanediol as an initiator were charged under a nitrogen stream. For 6 hours. After confirming that the total content of remaining ε-force prolactone and (5-valerolactone) was 2% by weight or less based on the total reaction mixture, gradually increase the degree of vacuum using a vacuum pump. Residual ε-force prolactone and <5-valerolactone were removed, thus obtaining a hydroxyl value of 57.9 KOHmgZg, an acid value of 0.2 KOHmgZg, a moisture content of 0.005% by weight, and a viscosity at 25 ° C of 2, A copolymerized lactone polyol having 10 OmPas and a number average molecular weight of 2,000 was obtained.

(Example 3)

243 g of the copolymerized lactone polyol obtained in Production Example 3, The binder for printing ink was prepared in the same manner as in Example 1 except that the chain extender was 57 g, the chain extender was 12.8 g of isophorone diamine, and the terminal sealant was 0.23 g of monoethanolamine. Was obtained. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 2,400 mPa's / 25. The number average molecular weight of the polyurethane resin was 44,500, and the isocyanate group concentration was 0.01% by weight or less.

<Production Example 4>

 A round bottom flask similar to that of Production Example 1 was charged with 518 parts of ε-force prolactone, 302 parts of δ-valero lactone, and 118 parts of 1,4-butanediol as an initiator, and heated at 180 ° C under a nitrogen stream. For 6 hours. After confirming that the total content of remaining ε-caprolactone and δ-valerolactone was 2% by weight or less with respect to the total reaction mixture, the degree of vacuum was gradually increased by a vacuum pump, and the remaining 8-force prolactone and δ-valerolactone were removed. Thus, a copolymerized lactone polyol having a hydroxyl value of 224.8 KOHmgZg, an acid value of 0.4 KOHmg / g, a water content of 0.003% by weight, a viscosity at 25 ° C of 56 OmPas, and a number average molecular weight of 500 was obtained. .

(Example 4)

157 g of the copolymerized lactone polyol obtained in Production Example 4, 144 g of isophorone diisocyanate, 32.0 g of isophorone diamine as a chain extender, and 0.57 g of monoethanolamine as a terminal blocking agent. A polyurethane resin solution as a binder for printing ink was obtained in the same manner as in Example 1 except that the above procedure was repeated. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 3,700 mPa · sZ25 ° C. The number average molecular weight of the polyurethane resin was 43,200, and the isocyanate group concentration was 0.01% by weight or less. Manufacturing example 5>

 In a round bottom flask similar to that of Production Example 1, 626 parts by weight of ε-force prolactone, 365 parts by weight of d-valerolactone, and 9 parts by weight of 1,4-butanediol as an initiator were charged, and then 180 ° under a nitrogen stream. Polymerization was carried out at C for 6 hours. After confirming that the total content of remaining ε-caprolactone and δ-valerolactone was 2% by weight or less with respect to the total reaction mixture, the degree of vacuum was gradually increased by a vacuum pump, and the remaining Ε one-strength prolactone and (5-valerolactone were removed. In this way, hydroxyl value 11.3 KOHmg / g, acid value 0.4 KOHmgZg, moisture content 0.007%, 25 viscosity 63, 10 OmP A copolymerized lactone polyol having a · s number average molecular weight of 10,000 was obtained.

(Example 5)

 132 g of the copolymerized lactone polyol obtained in Production Example 5, polyε-caprolactone (Braxcel 220, 0 «: value 56.1 KOHmg / g, manufactured by Daicel Chemical Industries, Ltd.) 132 g, isophorone diisocyanate 36 g, a chain extender of 8.1 g of isophoronediamine, and 0.115 g of monoethanolamine as a terminal blocking agent in the same manner as in Example 1, except that the binder was a printing ink ink. A polyurethane resin solution was obtained. The obtained polyurethane resin solution had a resin solid content of 30% by weight and a viscosity of 3,20 OmPas-25. The number average molecular weight of the polyurethane resin was 59,800, and the isocyanate group concentration was less than 0.01% by weight. Manufacturing example 6>

In the same round bottom flask as in Production Example 1, 612 parts by weight of ε-force prolactone, 357 parts by weight of δ-valerolactone, and 31 parts by weight of ethylene glycol as an initiator And polymerization was carried out at 180 ° C. for 6 hours under a nitrogen stream. Residual ε-force After confirming that the total content of prolactone and <5-valerolactone was 2% by weight or less based on the total reaction mixture, gradually increase the degree of vacuum using a vacuum pump and maintain Ε-force prolactone and δ-valerolactone were removed. Thus, a copolymerized lactone polyol having a hydroxyl value of 56.2 KOHmgZg, an acid value of 0.3 KOHmgZg, a water content of 0.007% by weight, a 25T viscosity of 260 OmPas and a number average molecular weight of 2,000 was obtained. .

(Example 6)

 98 g of the copolymerized lactone polyol obtained in Production Example 6, polyε-force prolactone (Braxel 220, Ο value 56. l KOHmg / g, Daicel Chemical Industries, Inc. 46 g, isophorone diisocyanate 36 g And as a chain extender

 A polyurethane resin solution as a binder for a printing ink was obtained in the same manner as in Example 1, except that 2.4 g and 0.222 g of monoethanolamine were used as a terminal blocking agent. The obtained polyurethane resin solution had a resin solid content of 30% by weight and a viscosity of 2,90 OmPa · s / 25 ° C. The number-average molecular weight of the polyurethane resin was 42,300 and the isocyanate group concentration was less than 0.01% by weight.

<Production Example 7>

In a round-bottom flask similar to that of Production Example 1, 815 parts by weight of ε-force prolactone, 126 parts by weight of δ-valerolactone, and 59 parts by weight of 1,6-hexanediol as an initiator were charged under a nitrogen stream. The polymerization was carried out at 180 for 6 hours. After confirming that the total content of remaining ε-force prolactone and δ-valerolactone was 2% by weight or less based on the total reaction mixture, gradually increase the degree of vacuum using a vacuum pump and maintain Ε-force prolactone and δ-valerolactone were removed. in this way Hydroxyl value 55.4 KOHmg / g, acid value 0.4 KOHmg / g, water content 0.005% by weight, viscosity at 25 ° C 2,90 OmPas s Copolymer lactone with molecular weight of 2,000 A polyol was obtained.

(Comparative Example 1)

 98 g of the copolymerized lactone polyol obtained in Production Example 7, 245 g of isophorone diisocyanate, 12.2 g of isophorone diamine as a chain extender, and 0.1 g of monoethanolamine as a terminal sealant. A polyurethane resin solution was obtained in the same manner as in Example 1 except that the amount was 22 g. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 3,30 OmPa · s / 25 ° C. The number average molecular weight of the polyurethane resin was 49,800, and the isocyanate group concentration was less than 0.01% by weight. Manufacturing example 8>

 The same round bottom flask as in Production Example 1 was charged with 58 parts by weight of ε-force prolactone, 783 parts by weight of δ-valerolactone, and 59 parts by weight of 1,6-hexanediol as an initiator. 18 (Polymerization was carried out for 6 hours at TC. It was confirmed that the total content of remaining ε-force prolactone and δ-valerolactone was 2% by weight or less based on the whole reaction mixture. Thereafter, the degree of vacuum was gradually increased by a vacuum pump to remove the remaining ε-force prolactone and <5-palerolactone, thus obtaining a hydroxyl value of 55.4 KOHmg / g, an acid value of 0.4 KOHmg / g, A copolymerized lactone boroliol having a water content of 0.006% by weight, a viscosity of 25 and a viscosity of 2,30 OmPa · s and a molecular weight of 2,000 was obtained.

(Comparative Example 2)

244 g of the copolymerized lactone polyol obtained in Production Example 8, isophorone diisocy A polyurethane resin solution was obtained in the same manner as in Example 1 except that the amount of phenolate was 56 g, the chain extender was 12.4 g of isophoronediamine, and the terminal sealant was 0.22 g of monoethanolamine. Was. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 2,30 OmPa-s / 25. The number average molecular weight of the polyurethane resin was 41,500, and the isocyanate group concentration was 0.01% by weight or less.

<Production Example 9>

 A round-bottomed flask similar to that of Production Example 1 was charged with 469 parts by weight of ε-prolactone, 274 parts by weight of <3-valerolactone, and 257 parts by weight of 1,4-butanediol as an initiator. Polymerization was performed at ° C for 6 hours. After confirming that the total content of remaining ε-force prolactone and <5-valerolactone was 2% by weight or less based on the total reaction mixture, gradually increase the degree of vacuum with a vacuum pump. Residual ε-caprolactone and <5-valerolactone were removed. Thus, a copolymerized lactone polyol having a hydroxyl value of 320.6 KOH mgZg, an acid value of 0.2 KOH mgZg, a water content of 0.008%, and a viscosity of 25 OmPa · s and a molecular weight of 350 was obtained.

(Comparative Example 3)

130 g of the copolymerized lactone polyol obtained in Production Example 9, 170 g of isophorone diisocyanate, 36.8 g of isophorone diamine as a chain extender, and 0.68 g of monoethanolamine as a terminal blocking agent A polyurethane resin solution was obtained in the same manner as in Example 1 except that the above conditions were satisfied. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 3,90 OmPa · s / 25 ° C. The number average molecular weight of the polyurethane resin was 38,700, and the isocyanate group concentration was 0.01% by weight or less. (Comparative Example 4)

122 g of the copolymerized lactone polyol obtained in Production Example 6, poly-ε one-strength prolactone (Braxel 220, 〇11 value 56.1 KOHmg / g, manufactured by Daicel Chemical Industries, Ltd.) 122 g, isophorone diisocyanate 56 g., isophorone diamine 12.2 lg as a chain extender and 0.22 g of monoethylamine as a terminal blocking agent, and a polyurethane resin solution was obtained in the same manner as in Example 1. Was done. The obtained polyurethane resin solution had a resin solid content concentration of 30% by weight and a viscosity of 280 OmPa-s / 25 ° C. The number average molecular weight of the polyurethane resin was 46,300, and the isocyanate group concentration was 0.01% by weight or less.

表 1中の略号は以下の通りである。

The abbreviations in Table 1 are as follows.

 Mn: Number average molecule of copolymerized lactone polyol]

1, 6—I-IG: 16-hexanediol 1,4-BG: 1,4-butanediol

 EG: Ethylene Dalicol

 CLM: ε-force prolactone monomer

 VLM: δ-Valerolactone monomer

(Preparation of ink)

 30 parts by weight of titanium white (rutile type), 50 parts by weight of the polyurethane resin solution obtained in Examples 1 to 6 and Comparative Examples 1 to 4, 10 parts by weight of ethyl acetate, and 10 parts by weight of isopropyl alcohol (IPA) Were mixed with a paint shaker to prepare a white printing ink. To 100 parts by weight of the obtained mixture, 35 parts by weight of ethyl acetate and 15 parts by weight of isopropyl alcohol were added to adjust the viscosity, thereby preparing 10 white printing inks as shown in Table 2.

(Preparation of laminate film and performance evaluation method)

The obtained 10 white printing inks were applied to the discharge treated surface of a 15 m thick corona discharge treated nylon film (NY) and a 11 x m thick polyethylene terephthalate using a No. 32 bar coater. (PET) and dried at 40-50 ° C to obtain a printed film with a coating thickness of about 10 / m. A polyurethane-based adhesive having a solid content of 25% by weight (TM-329 and CAT-88 of Toyo Morton Co., Ltd.) mixed on a printing surface of the printing film to a solid content of 25% by weight with ethyl acetate. After dilution and drying at a coating amount of 3 gZm ^2, a 60 / im polyethylene film was pressed with a press at 50 ° C. at 4 kgf / cm ² for 10 seconds to obtain a laminated film. The laminate strength (adhesive strength) of the laminate film thus obtained and the suitability for boiling at 100 ° C. were evaluated as follows. Table 1 shows the evaluation results.

Boiling aptitude (1) Evaluation by change in appearance of film The appearance change of the laminate film after boiling at 100 ° C for 30 minutes was observed.

 〇: There is no abnormality in the film.

 Δ: A very small part of the film has been delaminated or a slight amount of blister has occurred.

 X: Part of the film is delaminated or blistered.

 (2) Evaluation based on changes in laminate strength (adhesive strength)

 After boiling the laminate film at 100 for 30 minutes, cut it into 15 mm width, measure the T-peel strength (unit: g / 15 mm) at a speed of 30 OmmZ minutes with a peel tester, and compare it with the strength before boiling. .

 Redissolvability: Apply water-based printing ink to a glass plate at a solid content of 2 to 3 xm with Barco overnight, leave it at room temperature for 2 minutes to dry the ink surface half-dry, then 5% Aqueous ammonia solution was immersed in a mixed solution of ZI PA = 5 / l, and the solution was mixed with a glass rod to observe the resolubility of the ink coating film. The evaluation criteria are as follows.

〇: The coating film is redissolved.

 X: The coating film remains without being dissolved.

 Cellotape adhesion: Surface-treated polypropylene film (surface-treated PP), surface-treated polyester film (surface-treated PET), and surface-treated nylon film are coated with printing ink at a solid content of 2 to 3 / xm. It was applied overnight, dried at 60 ° C for 1 minute, and left at room temperature for 1 day. A cellophane tape (Nichiban, 12 mm width) was applied to the application surface, and the state of the application surface when one end of the cellophane tape was rapidly peeled off at right angles to the application surface was observed. The evaluation criteria are as follows.

A: The coating film does not peel off.

 〇: 80 to 100% of the coating film remains.

Δ: 50 to 80% of the coating film remains. X: less than 50% of the remaining coating film.

Blocking resistance: The coated and uncoated surfaces of the coated test piece (coated on PET film) obtained by the same method as in the cellophane adhesive test were superimposed at a temperature of 40 ° C and a humidity of 60% RH. A load of 0 kgf Zcm ² was applied, and after 24 hours, it was peeled off and the state of the surface was observed.

 Oil resistance: A coated specimen (coated on a PET film) obtained by the same method as in the cellophane adhesive test was immersed in rapeseed oil at 25 ° C for 24 hours, and the surface condition was observed. The evaluation criteria are as follows.

 :: No change in the surface of the coating film.

 〇: The gloss of the coating film was slightly reduced.

 Δ: The coating film has blisters.

 X: The coating film peeled off from the substrate.

 Water resistance: A coated test piece (coated on a PET film) obtained by the same method as the cellophane tape adhesion test was immersed in water at 25 ° C for 24 hours, and then a cellophane tape was stuck on the coated surface and one end of this cellophane tape was coated. In contrast, the state of the coated surface when the film was rapidly peeled off in the direction perpendicular to the direction was observed. The evaluation criteria are as follows.

 A: No change in the surface of the coating film.

 〇: The gloss of the coating film was slightly reduced.

 Δ: The coating film has blisters.

 X: The coating film peeled off from the substrate.

Laminating adhesiveness: surface treatment The printing ink was applied to the OPP film with a bar coater to a thickness of 2 to 3 Xm in solid content, dried at 60 ° C for 1 minute, and then left at room temperature for 1 day. An untreated polypropylene film (CPP) is superimposed on the coating surface, and 180 is heated with a heat sealer (Toyo Seiki Co., Ltd.). CX 2 kgf / cm ² × 1 second under the conditions of hot-melt compression bonding, followed by cooling to obtain a laminated film. From this, a test piece having a width of 15 mm was sampled, and the T peel strength (g) was measured by an autograph. Table 2

 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Laminate Strength (Before Wheel) PET 490 480 490 380 380 380 470 460 450 250 460 Laminate strength (before wheel) NY 650 610 630 510 510 530 610 590 600 260 180 Degree UP ill Shun) hi shelf 4bU 470 0 Sb 4ou 4dl) 4dU

 eon

Flat strength w v w 600 600 480 500 620 550 560 zoo loll

 変 化 〇 〇 〇 〇 厶 Δ 変 化 Appearance change o 〇

Laminate strength (after wheel) Y

Externalization 〇 〇 Ο 〇 o 〇 〇 O X X Redissolvability o ο o o X X X o Mouth 7 ~ Urr Ό U Ri X X

· Ϊ? Πτ- ⁰ PPT A Λ Separate tape Y Y ◎ ◎ ◎ 0 o ◎ 〇 〇 XX フ ツ ツ ツ ツ 油 油 油 〇 〇 〇 油〇 XX Water resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Laminate adhesive 120 120 120 100 100 120 120 120 70 60

Industrial applicability

 The binder for printing ink of the present invention and the printing ink composition using the binder have excellent adhesiveness and boil resistance to various plastic films such as polyester, nylon film, polyethylene, and polypropylene, which are to be printed. Is exhibited. The printing ink composition of the present invention can be preferably used as a one-component ink composition.

Claims

The scope of the claims 1. In a binder for a printing ink containing a polyurethane resin (D) obtained by reacting a polyol component (A), an isocyanate compound (B) and a chain extender (C), at least the polyol component (A) contains at least Using a polyol compound having two active hydrogen groups as an initiator, ring-opening copolymerization of ε-force prolactone and δ-valerolactone in a molar ratio of 20Ζ80 to 80Ζ20 results in a number average molecular weight of 400 to 20,000. A binder for printing ink, comprising: (a1) at least 40% by weight of the force S polyol component (A).  2. The binder for printing ink according to claim 1, wherein the chain extender (C) is a polyol compound or a polyamine compound having at least two active hydrogen groups.  3. A printing ink composition comprising the printing ink binder according to claim 1 or 2.  4. The printing ink composition according to claim 3, which is a one-pack type.