JPH0912956A - Binder for printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane resin as a binder for printing ink fully satisfying its adhesivity to all of the plastic films including polyolefin films and having processing suitability after printing. SOLUTION: This binder consists of a polyurethane resin obtained by reaction of a chain extender and/or reaction terminator with a hydroxyl and epoxy groups-contg. chlorinated polypropylene-based copolymer and a urethane prepolymer bearing isocyanate groups on both ends prepared from a polymeric polyol and an organic diisocyanate. The above-mentioned copolymer is obtained from a chlorinated polypropylene, a vinyl-based alcohol compound and vinyl- based epoxy compound. The polymeric polyol is composed of a polyester bearing hydroxyl groups on both ends 500-10000 in number-average molecular weight prepared from 3-methyl-1,5-pentanediol and adipic acid, a terephthalic acid-based polyester bearing hydroxyl groups on both ends 500-10000 in number-average molecular weight and another polyol >=500 in number-average molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyurethane resin suitable as a binder for printing inks.

[0002]

2. Description of the Related Art Polyurethane resins have been used as binders for printing inks. Japanese Patent Examination 5-641
No. 92, a hydrogenated polybutadiene having a molecular weight of 500 to 4000 and having a hydroxyl group at the terminal or a polyurethane resin formed from this and other polymeric diol, an alicyclic diisocyanate, a chain extender and, if necessary, a terminal blocking agent. A binder for printing inks consisting of a solvent solution of

[0003]

However, the conventional polyurethane-based printing inks are sufficiently satisfactory in blocking resistance, suitability for laminating, resistance to boil, and suitability for retort, but their adhesiveness to polyolefin film is still insufficient. It was

The present invention provides a polyurethane resin for a binder for a printing ink, which sufficiently satisfies the adhesiveness to all plastic films including a general-purpose polyolefin film and has processability after printing. The purpose is to do.

[0005]

In order to achieve the above object, the present invention provides a urethane prepolymer containing a hydroxyl group- and epoxy group-containing chlorinated polypropylene copolymer, a polymer polyol and an organic diisocyanate having isocyanate groups at both ends. A binder for a printing ink comprising a polyurethane resin obtained by reacting a polymer with a chain extender and / or a reaction terminator, wherein the hydroxyl group- and epoxy group-containing chlorinated polypropylene copolymer is chlorinated polypropylene and vinyl. A hydroxyl group- and epoxy group-containing chlorinated polypropylene copolymer obtained from a vinyl alcohol compound and a vinyl epoxy compound, wherein the polymer polyol is a number average obtained from 3-methyl-1,5-pentanediol and adipic acid. Molecular weight 500-100
00 hydroxyl group-containing polyester, number average molecular weight 5
00-10,000 terephthalic acid-based polyester having hydroxyl groups at both ends and a polyol having a number average molecular weight of 500 or more other than these, containing 50-95% by weight of the both-end hydroxyl group-containing polyester in a polyurethane resin, and the both ends Containing 1 to 10% by weight of a hydroxyl group-containing terephthalic acid polyester in a polyurethane resin,
The above-mentioned binder for printing ink.

The hydroxyl group- and epoxy group-containing chlorinated polypropylene copolymer used in the present invention is obtained by a radical reaction of chlorinated polypropylene, a vinyl alcohol compound and a vinyl epoxy compound. Specifically, for example, these are dissolved in an aromatic solvent, and a polymerization initiator is further added to cause a radical reaction. As the solvent, toluene, an aromatic solvent such as xylene, an ester solvent,
A ketone solvent, an alcohol solvent, an aliphatic solvent, a cyclic alicyclic solvent or the like may be used in combination. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and di-tert-butyl peroxide, and azonitriles such as azobisisobutyronitrile.

The chlorinated polypropylene is obtained by dispersing or dissolving crystalline polypropylene or amorphous polypropylene in a medium such as water or carbon tetrachloride, and applying pressure or normal pressure in the presence of a catalyst or irradiation of ultraviolet rays. 5
It is obtained by blowing chlorine gas in the temperature range of 0 ° C to 120 ° C. Chlorinated polypropylene obtained by oxidizing at least one or two or more selected from air, oxygen and ozone at the same time during chlorine blowing is a copolymerization reaction of chlorinated polypropylene, vinyl alcohol compound and vinyl epoxy compound. It is preferable for smooth progress.

Specific examples of the vinyl alcohol compound include allyl alcohol, hydroxyethyl acrylate, 1-hydroxy-2-ethylhexyl acrylate, cyclohexanedimethanol monoacrylate, and 4
-Hydroxybutyl acrylate and the like, and ε-caprolactone adducts thereof and the like.

Specific examples of vinyl epoxy compounds include vinyl-epoxy ethers such as vinyl glycidyl ether and vinylbenzyl glycidyl ether, vinyl epoxides such as glycidyl acrylate and glycidyl methacrylate.
There is an epoxy ester.

The number average molecular weight of the chlorinated polypropylene type copolymer containing hydroxyl group and epoxy group is from 1000 to 100.
00 is preferable, and 1000 to 5000 is particularly preferable.
When the number average molecular weight is less than 1000, the adhesion to the polyolefin film becomes poor. On the other hand, when it exceeds 10,000, the durability and the adhesion to the polyethylene terephthalate film and the nylon film become poor.

The chlorine content is 10 to 50% by weight in the chlorinated polypropylene copolymer containing hydroxyl groups and epoxy groups.
Is preferred, and particularly preferably 10 to 30% by weight. When the chlorine content is less than 10% by weight, compatibility with high molecular polyols and solvents is lost when synthesizing a polyurethane resin, and a chlorinated polypropylene copolymer skeleton is hardly introduced into the polyurethane resin skeleton and free. Therefore, the storage stability becomes poor. On the other hand, if it exceeds 50% by weight, dechlorination is likely to occur from the chlorinated polypropylene copolymer skeleton, resulting in poor durability.

The number of hydroxyl groups introduced into the chlorinated polypropylene copolymer skeleton is preferably 1.0 to 2.0, and more preferably 1.2 to 1.8 on average per molecule. When the number of introduced hydroxyl groups is less than 1.0, the chlorinated polypropylene copolymer skeleton is hardly introduced into the polyurethane resin skeleton, and the polyurethane resin skeleton is blended with the polyurethane resin, resulting in poor storage stability. . If the number exceeds 2.0, gelation occurs during synthesis of the polyurethane resin, making it difficult to obtain the resin.

The amount of epoxy groups introduced into the chlorinated polypropylene copolymer skeleton is 100 to 1000 g / eq.
iv is preferable, and 200 to 800 g / eqiv is particularly preferable. When the epoxy group introduction amount is less than 100 g / eqiv, the polyurethane resin filling container is easily corroded or the resin is easily colored. When it exceeds 1000 g / eqiv, it reacts with an organic diamine which is a chain extender in producing a polyurethane resin, and gelation is likely to occur.

Specific examples of the chlorinated polypropylene-based copolymer containing hydroxyl group and epoxy group include:
Toyo Kasei's Hardlen B-13, B-400
There is a Hardlen B series such as 0.

The amount of the hydroxyl group- and epoxy group-containing chlorinated polypropylene copolymer used is preferably 1 to 20% by weight, more preferably 3 to 10% by weight, in the polyurethane resin. . When the content of the chlorinated polypropylene-based copolymer containing hydroxyl groups and epoxy groups is less than 1% by weight, the adhesion to the polyolefin film becomes poor. If it exceeds 20% by weight, the durability and the adhesiveness to a plastic film other than the polyolefin film become poor.

The polymeric polyol used in the present invention is
It is a mixture of polyesters having hydroxyl groups at both ends obtained from 3-methyl-1,5-pentanediol as an active hydrogen component and adipic acid as an acid component, terephthalic acid type polyesters having hydroxyl groups at both ends, and a polyol other than them.

The number average molecular weight of the polyester having hydroxyl groups at both ends is 500 to 10,000, and 2,000 to 50.
00 is preferable. When the number average molecular weight is less than 500,
The cohesive force in the polyurethane resin becomes excessively large, resulting in poor adhesiveness. When it exceeds 10,000, the cohesive force in the polyurethane resin becomes excessively small and the blocking resistance becomes poor. Specific examples of this compound include Kuraray P-510, 1010, 151 manufactured by Kuraray Co., Ltd.
0, 2010, 3010, 4010, 5010 can be mentioned.

The amount of the polyester having hydroxyl groups at both ends is 50 to 95% by weight, preferably 60 to 80% by weight, in the polyurethane resin. When the content of the polyester having hydroxyl groups at both ends is less than 50% by weight in the polyurethane resin,
Poor ink adhesion. If it exceeds 95% by weight,
Poor blocking resistance.

The number average molecular weight of the terephthalic acid type polyester having hydroxyl groups at both ends is 500 to 10,000,
2000-5000 are preferable. Number average molecular weight is 500
When it is less than the above range, the cohesive force in the polyurethane resin becomes excessively large, resulting in poor adhesiveness. When it exceeds 10,000, the flexibility of the polyurethane resin is reduced and the flexibility is lost.

This terephthalic acid type polyester having hydroxyl groups at both ends is, for example, a dehydration condensation polymerization of a compound having two active hydrogen groups such as glycol and amino alcohol as an active hydrogen component and a dicarboxylic acid containing at least terephthalic acid as an acidic component. Alternatively, it can be obtained by dehydrochlorination condensation polymerization of a compound having two active hydrogen groups and a dichloride containing at least terephthalic acid dichloride. As a specific constituent component, the raw material dicarboxylic acid of dicarboxylic acid or dicarboxylic acid dichloride,
In addition to terephthalic acid, isophthalic acid, orthophthalic acid,
There are hydrogenated phthalic acid, adipic acid, azelaic acid, sebacic acid and the like. Specific examples of glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl- 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-
Hexanediol, 2,2,4-trimethyl-1,3-
Propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol,
2-n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, N-methyl-diethanolamine, N-phenyl-dipropanolamine and the like, Specific examples of amino alcohols include monoethanolamine and the like.

The terephthalic acid type polyester having hydroxyl groups at both ends is used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight in the polyurethane resin. If it is less than 1% by weight, blocking resistance becomes poor. When it exceeds 10% by weight, the flexibility of the polyurethane resin is reduced and the flexibility is lost.

Polyols other than the both-end hydroxyl group-containing polyester and the both-end hydroxyl group-containing terephthalic acid polyester have a number average molecular weight of 500 or more. The average number of functional groups of this polyol is preferably 2 to 3. This polyol may contain a carboxyl group, a tertiary amino group, a sulfonic acid group and the like, and salts thereof, and any of those used in polyurethane chemistry can be used. This polyol may be composed of a single polyol or may be composed of a plurality of polyols having an average number of functional groups of 2 to 3.

The organic diisocyanates used in the present invention are all known organic diisocyanates, but organic diisocyanates containing at least a side chain alkyl group-containing aliphatic diisocyanate are preferred, and especially side chain alkyl group-containing aliphatic diisocyanates alone are used. Preferably there is. The amount of the side chain alkyl group-containing aliphatic diisocyanate used is 1 to 2 in the polyurethane resin.
The amount is preferably 0% by weight, particularly preferably 3 to 10
It is the amount that becomes the weight%. If it is less than 1% by weight, the adhesiveness will be poor. If it exceeds 20% by weight, blocking resistance becomes poor.

Specific examples of the aliphatic diisocyanate containing a side chain alkyl group include 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and 2,2,4-trimethylhexane-1. , 6
-Diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate and the like and mixtures thereof.

Examples of the organic diisocyanate that can be used in combination with the aliphatic diisocyanate containing a side chain alkyl group include 1,5-naphthylene diisocyanate and 4,4 '.
-Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, paraphenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-
Aromatic diisocyanates such as 2,6-diisocyanate, ortho-xylylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate and other yellowing-resistant organic diisocyanates, isophorone diisocyanate, alicyclic diisocyanates such as 4,4′-dicyclohexylmethane diisocyanate , Hexamethylene diisocyanate, lysine diisocyanate, etc., and aliphatic diisocyanates in which an alkyl group is not directly bonded to a side chain, or a mixture thereof.

The chain extender which can be used in the present invention includes organic diamines and glycols having a molecular weight of less than 500. Specifically, as the organic diamine, there are ethylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexyldiamine and the like and mixtures thereof, and as the glycol, ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3- Pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-
Methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol,
2,2-diethyl-1,3-propanediol, 2-n
-Butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A and the like.

Examples of the reaction terminator which can be used in the present invention include monoalcohol, monoamine, amino alcohol and the like. As the monoalcohol, methanol, ethanol, propanol, isopropanol,
2-ethylhexanol and the like. Monoamines include primary amines such as ethylamine, propylamine and butylamine, and secondary amines such as diethylamine and dibutylamine.
There are secondary amines. Examples of amino alcohols include monoethanolamine and diethanolamine.

As the reaction catalyst for synthesizing the urethane prepolymer having isocyanate groups at both ends and the polyurethane resin in the present invention, known so-called urethanization catalysts can be used. Specifically, there are organic metal compounds such as dioctyltin dilaurate, organic amines such as triethylenediamine, and salts thereof.

As the solvent used in the present invention, aromatic solvents such as toluene and xylene which are often used as solvents for printing inks, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone are used. Solvents, alcohol-based solvents such as methanol, ethanol, and isopropanol, can be used individually or as a mixed solvent.

In producing a polyurethane resin, first, a high molecular polyol and a chlorinated polypropylene copolymer containing a hydroxyl group and an epoxy group are mixed, and a solvent such as a ketone or ester having no active hydrogen or an aromatic hydrocarbon is mixed. Dilute appropriately with. An organic diisocyanate is added to this mixed solution, and, for example, after a urethanization catalyst is added, the temperature is adjusted to 30 to
The reaction is carried out in the range of 100 ° C. for several hours to synthesize a solution of urethane prepolymer containing isocyanate groups at both ends. At this time, the molar ratio of NCO group / OH group is 1.1 to
2.5 is preferable, and 1.5 to 2.0 is particularly preferable. N
When the CO group / OH group molar ratio is less than 1.1, durability and blocking resistance are poor. When it exceeds 2.5, the solubility in a solvent and the adhesion as an ink become poor.

A chain extender and / or a reaction terminator, preferably a chain extender and a reaction terminator, is added to the solution of the urethane prepolymer having isocyanate groups at both ends obtained in this way, for example, 30 to 50. By reacting in the temperature range of ° C until the isocyanate group disappears, the polyurethane resin used as the binder for the intended printing ink can be obtained.

The number average molecular weight of the polyurethane resin thus obtained is preferably 8,000 to 100,000, and particularly preferably 10,000 to 50,000. When the number average molecular weight of the polyurethane resin is less than 8,000, the durability and blocking resistance are poor, and when it exceeds 100,000, the fluidity of the ink and the pigment dispersibility are poor.

In the case of producing a printing ink using this polyurethane resin, a diluent solvent and various pigments are added and the meat is smelted and dispersed. If necessary, various additives and vinyl chloride are added.
A secondary binder resin such as vinyl acetate copolymer and nitrification cotton can be added.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 A 2 liter four-necked flask equipped with a stirrer, a thermometer, an Aren cooling tube, and a nitrogen gas introducing tube was placed in a number average molecular weight of 50.
Terephthalic acid-based polyester (A) having a number average molecular weight of 2000 and having a number average molecular weight of 2000 (418 g), 3-methyl-1,5-pentane adipate (trade name: Kurapol P-5010, manufactured by Kuraray Co., Ltd.) (Terephthalic acid / isophthalic acid = 1/1, neopentyl glycol / ethylene glycol = 1/1 by molar ratio) in toluene solution (solid content 70%) (TPA-based PES (A)) 40
Polyester diol (PBA-1) composed of 1,4-butanediol having a number average molecular weight of 1,000 and adipic acid.
000) in a toluene solution of a chlorinated polypropylene-based copolymer containing hydroxyl groups and epoxy groups (solid content: 40).
%, Trade name: Hardlen B-4000, manufactured by Toyo Kasei Kogyo Co., Ltd., 75 g, and 143 g of toluene were charged and uniformly stirred. 2,2,4-trimethylhexamethylene-1,6-diisocyanate and 2,2,4-trimethylhexamethylene were added to this polyol solution.
Mixture of 4,4-trimethylhexamethylene-1,6-diisocyanate (trade name: Vestanat TMDI,
59 g of Daicel-Huls Co., Ltd. and 0.08 g of dioctyltin dilaurate as a urethanization catalyst were added and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 500 g of toluene and 420 g of methyl ethyl ketone were added and homogenized, and then a mixed solution of 280 g of isopropanol, 22 g of isophoronediamine and 1 g of monoethanolamine was added all at once, and the reaction was carried out at 40 ° C. until the isocyanate groups disappeared. Then, a polyurethane resin solution PU-1 was obtained. PU-1 has a solid content of 30 wt.
%, The viscosity was 1000 cP (25 ° C.), and the number average molecular weight of the polyurethane resin was 21,000. These are summarized in Table 1.

Synthetic Example 2 An apparatus similar to Synthetic Example 1 was loaded with Clapol P-5010.
427 g of terephthalic acid type polyester (B) containing hydroxyl groups at both ends having a number average molecular weight of 2000 (terephthalic acid / isophthalic acid / adipic acid = 1/1/1, neopentyl glycol / ethylene glycol = 1/1 in molar ratio) Toluene solution (solid content 70%) (TPA-based PES (B))
Of 40 g, a number average molecular weight of 1 obtained from the deethanolization reaction of 1,6-hexanediol and diethyl carbonate.
000 polycarbonate diol (HG-PCD-1
000) 43 parts, HARDREN B-4000 75 g,
Toluene (143 g) was charged and stirred uniformly. To this polyol solution, 48 g of 3-methylpentane-1,5-diisocyanate (3MPDI) and 0.08 g of dioctyltin dilaurate were added and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. It was To this prepolymer solution, add 50 parts of toluene.
After 0 g and 420 g of methyl ethyl ketone were added and homogenized, a mixed solution of 280 g of isopropanol, 22 g of isophoronediamine and 1 g of monoethanolamine was added all at once, and the mixture was reacted at 40 ° C. until the isocyanate groups disappeared, and the polyurethane resin solution PU- Got 2. P
U-2 has a solid content of 30 wt% and a viscosity of 1100 cP (2
5 ° C), the number average molecular weight of the polyurethane resin is 22,000
Met. These are summarized in Table 1.

Synthetic Example 3 The same apparatus as in Synthetic Example 1 was loaded with Clapol P-5010.
421 g, TPA-based PES (A) 40 g, and polycaprolactone diol having a number average molecular weight of 1000 (PCL-
1000) 42g, HARDREN B-4000 75
g and 143 g of toluene were charged and stirred uniformly. To this polyol solution, 24 g of 2-methylpentane-1,5-diisocyanate (2MPDI), 32 g of isophorone diisocyanate (IPDI), and 0.08 g of dioctyltin dilaurate as a urethane-forming catalyst were added.
The reaction was carried out at 4 ° C for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution was added 500 g of toluene and 42 g of methyl ethyl ketone.
After adding 0 g and homogenizing, further 280 g isopropanol
21 g of isophoronediamine and monoethanolamine 2
A mixed solution with g was added all at once, and the mixture was reacted at 40 ° C. until the isocyanate groups disappeared to obtain a polyurethane resin solution PU-3. PU-3 had a solid content of 30 wt%, a viscosity of 1050 cP (25 ° C.), and a polyurethane resin having a number average molecular weight of 20,000. These are summarized in Table 1.

Synthetic Comparative Example 1 40 g of TPA-based PES (A), 42 g of PBA-1000, and a polyester diol of 1,6-hexanediol and adipic acid having a number average molecular weight of 5000 were placed in the same apparatus as in Synthetic Example 1. (PHA-5000) 418
g, HARDREN B-4000 (75 g), toluene (14)
3 g was charged and stirred uniformly. To this polyol solution, 59 g of Vestanat TMDI and 0.08 g of dioctyltin dilaurate as a urethane-forming catalyst were added, and the mixture was heated to 80 ° C.
Was reacted for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 500 g of toluene and 420 of methyl ethyl ketone were added.
After adding g to make it uniform, 280 g of isopropanol, 22 g of isophoronediamine and 1 g of monoethanolamine are further added.
The mixed solution with and is added all at once and reacted at 40 ° C. until the isocyanate group disappears, and the polyurethane resin solution P
U-4 was obtained. PU-4 had a solid content of 30 wt%, a viscosity of 1100 cP (25 ° C.), and a polyurethane resin having a number average molecular weight of 22,000. These are summarized in Table 1.

Synthesis Comparative Example 2 An apparatus similar to that used in Synthesis Example 1 was loaded with Clapol P-5010.
450 g, TPA-based PES (B) 43 g, PCL-
45 g of 1000 and 187 g of toluene were charged and uniformly stirred. 50 g of 2MPDI in this polyol solution,
0.08 g of dioctyltin dilaurate was added as a urethanization catalyst and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 500 g of toluene and 420 g of methyl ethyl ketone were added and homogenized, and then a mixed solution of 280 g of isopropanol, 23 g of isophoronediamine, and 2 g of monoethanolamine was added all at once.
The reaction was carried out at 40 ° C. until the isocyanate group disappeared to obtain polyurethane resin solution PU-5. PU-5 has a solid content of 30 wt%, a viscosity of 1700 cP (25 ° C.),
The number average molecular weight of the polyurethane resin was 30,000. These are summarized in Table 1.

Synthesis Comparative Example 3 An apparatus similar to that of Synthesis Example 1 was loaded with Clapol P-5010.
507 g, a toluene solution of hydroxyl group-containing chlorinated polypropylene (solid content 40%, trade name: HARDREN B-404
1. Toyo Kasei Co., Ltd. 75 g, toluene 15
5 g was charged and stirred uniformly. Add I to this polyol solution
PDI 46g, dioctyltin dilaurate 0.0
8 g was added and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 500 g of toluene and 420 g of methyl ethyl ketone were added and homogenized, and then a mixed solution of 280 g of isopropanol, 16 g of isophoronediamine and 1 g of monoethanolamine was added all at once, and the reaction was continued at 40 ° C. until the isocyanate groups disappeared. Then, a polyurethane resin solution PU-6 was obtained. The solid content of PU-6 is 3
0 wt%, the viscosity was 1100 cP (25 ° C.), and the number average molecular weight of the polyurethane resin was 23000. These are summarized in Table 1.

Synthetic Comparative Example 4 The same apparatus as in Synthetic Example 1 was loaded with Clapol P-5010.
507 g, HARDREN B-4041 75 g, bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 5.4 g, and toluene 155
g, and stirred uniformly. IP to this polyol solution
46 g DI, 0.08 dioctyltin dilaurate
g, and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 500 g of toluene and 420 g of methyl ethyl ketone were added and homogenized, and then a mixed solution of 280 g of isopropanol, 16 g of isophoronediamine and 1 g of monoethanolamine was added all at once, and the reaction was continued at 40 ° C. until the isocyanate groups disappeared. Then, a polyurethane resin solution PU-7 was obtained. The solid content of PU-7 is 30
%, the viscosity was 1100 cP (25 ° C.), and the number average molecular weight of the polyurethane resin was 23000. These are summarized in Table 1.

Synthesis Comparative Example 5 An apparatus similar to that used in Synthesis Example 1 was loaded with Krapol P-5010.
415 g, TPA-based PES (B) 40 g, PCL-
42 g of 1000, 75 g of Hardlen B-4041,
Toluene (143 g) was charged and stirred uniformly. To this polyol solution, 62 g of IPDI and 0.08 g of dioctyltin dilaurate as a urethanization catalyst were added, and the mixture was heated to 80 ° C.
Was reacted for 4 hours to obtain a urethane prepolymer solution containing isocyanate groups at both ends. To this prepolymer solution, 500 g of toluene and 420 of methyl ethyl ketone were added.
After adding g to make it uniform, 280 g of isopropanol, 21 g of isophoronediamine and 2 g of monoethanolamine
The mixed solution with and is added all at once and reacted at 40 ° C. until the isocyanate group disappears, and the polyurethane resin solution P
U-8 was obtained. The solid content of PU-8 was 30 wt%, the viscosity was 1200 cP (25 ° C.), and the number average molecular weight of the polyurethane resin was 25,000. These are summarized in Table 1.

[0043]

[Table 1]

[Polyurethane resin solution temporal stability test]
Fill a tin with PU-1 to 8 and store at 25 ° C and 50 ° C for 1 month. After one month, the state of corrosion of the can and the degree of coloring of the resin solution were observed. As for the evaluation, regarding corrosion of cans, those in which no corrosion was observed were evaluated as ○, and those in which corrosion was observed were evaluated as ×.
Displayed as Regarding the coloring of the resin solution, the one in which the coloring did not proceed was indicated by ◯, and the one in which the coloring proceeded was indicated by x. Table 2 summarizes these results.

[0045]

[Table 2]

Examples 1 to 3 and Comparative Examples 1 to 5 PU-obtained in Synthesis Examples 1 to 3 and Synthesis Comparative Examples 1 to 5
White inks were prepared using 1-8. The composition of the white ink is as shown below. Polyurethane resin solution 25.0 g Titanium oxide 22.5 g Toluene 19.3 g Methyl ethyl ketone 22.2 g Isopropanol 10.5 g White inks using PU-1 to 3 were used in Examples 1 to 3 and P, respectively.
White inks using U-4 to 8 are referred to as Comparative Examples 1 to 5, respectively. An ink performance test as shown below was carried out for each white ink. The results are summarized in Table 3.

[Ink Performance Test] 1. Adhesiveness Each ink is gravure printing machine, the discharge treated surface of corona discharge treated stretched polypropylene (OPP) film of thickness 15μ, the discharge treated surface of corona discharge treated polyethylene terephthalate (PET) film of thickness 11μ, or the thickness A 15 μ corona discharge treated nylon (NY) film, which had been subjected to printing on the discharge treated surface, was left for 1 day, and a cellophane tape was attached to the printed surface, and this was rapidly peeled off.
The evaluation was ◎, 80 when the printed film did not come off at all.
%, The remaining 50% to 80% was indicated as Δ, and the remaining 50% or less was indicated as x.

2. Blocking resistance After each ink is printed on various films with a gravure printing machine, left for 1 day, and then stacked on the front and back sides with a blocking tester to apply a load of 5 kgf / cm ² and
The blocking resistance was evaluated under the conditions of 0 ° C. × 80 RH% × 24 hours. In the evaluation, those that peeled without any resistance when peeled off and the printed surface did not fall off were evaluated as ○, and there was some resistance, but the printed surface did not fall off, △, the resistance was large and the printed surface was greatly removed. Was displayed as x.

3. Lamination Suitability The lamination suitability test was evaluated by the heat seal strength with an OPP film / ink / unstretched polypropylene (CPP) film. Each ink was printed on a corona-treated OPP film with a gravure printing machine, allowed to stand for 1 day, then overlaid with an untreated CPP film, and then placed at 180 ° C x 0.
Heat sealing was performed under the conditions of 5 seconds × 3 kgf / cm ² .
After heat-sealing, it was left for 1 day, cut into a width of 15 mm, and peel strength was measured to obtain heat-sealing strength.

[0050]

[Table 3]

[0051]

As described above, according to the present invention, excellent stability over time, pigment dispersibility, various coating performances and printability are satisfied, and particularly good adhesion to all kinds of plastic films including polyolefin films. It has become possible to provide a binder for printing inks that exhibits properties and satisfies various processing suitability after printing such as blocking resistance and laminating suitability.

Claims (1)

[Claims] 1. A urethane prepolymer having hydroxyl groups and epoxy groups, a chlorinated polypropylene copolymer having hydroxyl groups and an epoxy group, a polymer polyol and an organic diisocyanate, which have isocyanate groups at both ends, is reacted with a chain extender and / or a reaction terminator. A binder for a printing ink comprising a polyurethane resin obtained, wherein the hydroxyl group- and epoxy group-containing chlorinated polypropylene-based copolymer contains a hydroxyl group and an epoxy group obtained from a chlorinated polypropylene, a vinyl alcohol compound and a vinyl epoxy compound. It is a chlorinated polypropylene copolymer, and the polymer polyol is a number average molecular weight of 50 obtained from 3-methyl-1,5-pentanediol and adipic acid.
0 to 10000 both-end hydroxyl group-containing polyester, number-average molecular weight 500 to 10000 both-end hydroxyl group-containing terephthalic acid polyester, and other number-average molecular weight 5
50 to 95% by weight of the polyester having hydroxyl groups at both ends in a polyurethane resin, which is composed of a polyol of 00 or more.
The binder for a printing ink, which contains the terephthalic acid-based polyester containing hydroxyl groups at both ends in a polyurethane resin in an amount of 1 to 10% by weight.