JPH04209673A - Binder for printing ink, and printing ink composition - Google Patents

Abstract

PURPOSE:To improve the adhesiveness to various plastic films and the adaptability to laminating, boiling and retorting by using a specified polyurethane modified with chlorinated PP as principal component. CONSTITUTION:A chlorinated PP component (a) having 1.5 to 4 hydroxyl groups on the average in the molecule, a polymeric polyol (b), and a diisocyanate compound (c) in an amount sufficient to provide an equivalent ratio of all the hydroxyl groups of components (a) sand (b) to the NCO group of component (C) of 1:(1.3 to 3.0) are made to react to give a urethane prepolymer. This prepolymer is allowed to react with a chain extender in a solvent, if necessary, in the presence of a chain terminator to give a solution having a viscosity of 50-100,000cPs at 25 deg.C and containing 15-60wt.% (in terms of solids) polyurethane modified with chlorinated PP and having a number-average molecular weight of 5,000 to 100,000. This solution is mixed, if necessary, with a resin compatible with the modified polyurethane to give the title binder.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a binder for printing ink and a printing ink. More specifically, the present invention relates to a printing ink binder particularly useful as a coating for plastic films, plastic sheets, or synthetic resin molded articles, and the printing ink composition.

[Conventional technology]

In recent years, with the diversification of packaged items and the advancement of packaging technology,
Various types of plastic films have been developed as packaging materials, and those suitable for the object to be packaged are being appropriately selected and used. Furthermore, when plastic films are used as packaging materials, printing is applied to the plastic films for decoration or surface protection. is increasingly required. In particular, printing inks have a wide range of adhesion properties to various composite films for the beautification and luxury of packaging containers.
Furthermore, suitability for various post-processing processes, such as suitability for laminating, boiling, and retorting, is becoming necessary. -H, methods such as gravure printing and flexographic printing are used for plastic films, etc., but in the case of film printing as packaging materials, most of them are rolled-up methods, so
Printing ink is required to dry quickly. Further, when used as food packaging, it is particularly required that residual solvent be small. In order to improve the performance of packaging materials, dry lamination or extrusion lamination may be applied after printing. In particular, films such as polyester and nylon are superior in strength and airtightness to other films, so they are laminated with polyethylene film, polypropylene film, etc. In this case, urethane-based film, etc. Use adhesive, and in the case of extrusion lamination, use an anchor coat agent. Furthermore, an aluminum foil may be interposed in the middle, and the packaging material may be boiled or retorted. In addition, in the field of packaging materials based on transparent substrates, where strength up to retort processing is not required, laminates are used in which stretched polypropylene (OPP) is used as a base film and is directly coated with molten polypropylene without using an anchor coating agent. A processing method (PP direct lamination) is also used. In order to carry out such post-processing, the printing ink used in the preliminary stage is required to have not only adhesion and printing suitability for various base films, but also suitability for each post-processing. The suitability of each type of printing ink is determined primarily by the binder used in the printing ink. Conventionally, printing inks used for polyester films have been those with a thermoplastic polyester resin as a binder, and for nylon films and polyester films, two-component type reactive inks of polyester resins having hydroxyl groups and isocyanate compounds have been used. Ink is used. Recently, printing inks using polyurethane as a binder have also been used as they have wide applicability to nylon, polyester, and other base films. On the other hand, for polyolefins to which PP direct lamination is applied, printing inks using chlorinated polyolefins with a relatively low degree of chlorination, such as chlorinated polypropylene, as a binder are used. However, printing inks using thermoplastic polyester resins not only have limited base films, but also have insufficient drying properties and have problems with workability such as blocking.
Two-component ink is reactive, so it has a short pot life.
There are various operational constraints and economic losses such as disposal of unused ink. In addition, printing inks that use polyurethane as a binder have excellent adhesion to polyester films and nylon films, but have insufficient adhesion to general-purpose polyolefin films such as polyethylene and polypropylene films. There is also the problem that lamination processing suitability, especially PP direct lamination, is insufficient. On the other hand, printing inks using chlorinated polyolefin as a binder exhibit good adhesion to polyolefin films, but they do not have sufficient adhesion to polyester or nylon films, which limits the base film. Although it has suitability for PP direct lamination, it does not have boilability or retort suitability, so its uses are limited. Furthermore, chlorinated polyolefin and polyurethane are not compatible with each other, making it difficult to use a mixture of the two. As mentioned above (conventional binders for printing inks have limitations on the base film, or even if they have versatility with respect to the base film, they have insufficient adhesion, and cannot be laminated or boiled). It did not have sufficient suitability for retort processing.Therefore, it is necessary to manufacture printing inks containing binders suitable for each type of base film, various lamination processing, retort processing, etc. This caused major problems in the ink manufacturing process, printing process, and inventory management of these materials and inks.

[Problem to be solved by the invention] The present invention relates to a printing ink binder that has excellent adhesion to various plastic films such as polyester, nylon, polyethylene, and polypropylene as printing substrates, and has excellent suitability for lamination processing, boiling processing suitability, and retorting processing suitability. The purpose of the present invention is to provide a printing ink composition. [Means to solve the problem]

As a result of intensive studies to solve the problems of the prior art, the present inventors discovered that a specific modified polyurethane having a chlorinated polypropylene skeleton in the molecule can solve all of the problems of the prior art. The present invention has been completed.That is, the present invention consists of the following: (1) A chlorinated polypropylene component and a polymeric polyol component having an average of 1.5 to 4 hydroxyl groups in the molecule, in an amount of 13 to 1 equivalent of these total hydroxyl groups. The prepolymer (
1) A binder for printing ink, characterized in that it mainly contains a chlorinated polypropylene-modified polyurethane obtained by polymerizing it using a chain extender. ■ A chlorinated polypropylene component having an average of 1.5 to 4 hydroxyl groups in the molecule and a diisocyanate compound at a ratio of 1.3 to 3.0 equivalents of diisocyanate compound per equivalent of hydroxyl group in the chlorinated polypropylene component. The prepolymer ([1) obtained by reacting the polymeric polyol component and the diisocyanate compound in an amount of 1 diisocyanate compound per equivalent of hydroxyl group in the polyol component. A prepolymer ([
1) A binder for printing ink, characterized in that it mainly contains a chlorinated polypropylene-modified polyurethane obtained by polymerizing a mixture with 1) using a chain extender, and 1) the chlorinated polypropylene described in 2 or 3 above This invention relates to a printing ink containing modified polyurethane as a main binder. In the present invention, the main binder is a chlorinated polypropylene-modified polyurethane obtained by further polymerizing a prepolymer (1) obtained by urethanizing a specific chlorinated polypropylene component having a hydroxyl group and a high-molecular polyol component with a chain extender. It is mandatory to use it as Furthermore, in the present invention, it is essential to use a chlorinated polypropylene-modified polyurethane obtained by polymerizing a mixture of prepolymer (l) and prepolymer (m) with a chain extender as the main binder. . The chlorinated polypropylene having an average of 1.5 to 4 hydroxyl groups in one molecule (hereinafter referred to as modified chlorinated PP component), which is a constituent component of the prepolymer (1) and (IT), is a commercially available chlorinated polypropylene. and a compound having a hydroxyl group and a radically polymerizable double bond by a known method. Here, the degree of chlorination of the raw material chlorinated polypropylene is usually 2.
It is preferably from 0 to 60, particularly preferably from 25 to 45. If it is less than 20, the solubility in organic diaphragms decreases,
If it exceeds 60, the adhesion to polyolefins and other synthetic resins will decrease when used as a modified chlorinated PP component. In addition, compounds having a hydroxyl group and a radically polymerizable double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate,
Examples include -hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, and 1°4-butynediol. The number average molecular weight of the obtained modified chlorinated PP component is usually 50.
0 to 50,000, preferably 700 to 30,000. If it is less than 500, the solubility in the solvent tends to decrease, and if it exceeds 50,000, not only the solubility but also the transparency of the film becomes poor, which is not preferable. As the high-molecular polyol component which is a constituent component of prepolymers (I) and (2), various known ones known as high-molecular polyol components of polyurethane are used for -H. For example, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc. Neck: ethylene glycol, diethylene glycol, triethylene glycol, 1°2-
Propanediol, 1,3-propanediol, 1,3
-butanediol, 1,4-butanediol, neopentyl glycol, bentanediol, 3-methyl-1,
Various known saturated and unsaturated low molecular weight glycols such as 5-bentanediol, 1,6-hexanediol, octanediol, 1,4-butynediol, dipropylene glycol or n-butyl glycidyl ether, 2
- Alkyl glycidyl ethers such as ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as persatic acid glycidyl ester, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, etc. acid, malonic acid,
Glutaric acid, pimelic acid, azelaic acid, sebacic acid,
Polyester polyols obtained by dehydration condensation of dibasic acids such as superric acid or their corresponding acid anhydrides, dimer acids, etc. - Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds: Other polycarbonate polyol marks , polybutadiene glycols, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, and various other known polymer polyols that are generally used in the production of polyurethane. In addition, in the case of a polymer polyol obtained from glycols and dibasic acid among the polymer polyol components,
Up to 5 mol% of the glycols can be substituted with the following various polyols. For example, glycerin, trimethylolpropane, trimethylolethane, 1,2
．． Examples include 6-hexanediol, 1,2,4-butanetriol, sorbitol, and pentaerythritol. The number average molecular weight of the polymeric polyol component is appropriately determined in consideration of the solubility, drying properties, blocking resistance, etc. of the resulting polyurethane, and is usually in the range of about 700 to 10,000, preferably in the range of 1000 to 6,000. It is better to do so. When the number average molecular weight is less than 700, printability tends to decrease due to a decrease in solubility;
If it exceeds 0, drying properties and blocking resistance tend to decrease. In the present invention, 5 prepolymers (I), (II) and (II)
As the diisocyanate compound which is a component in I), various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1
．． 5-naphthylene diisocyanate, 4.4'-diphenylmethane diisocyanate, 4.4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1 .4
-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2.2.4-1-dimethylhexamethylene diisocyanate, 2,4.4 -Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, inphorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(methyl isocyanate)
Representative examples thereof include cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate obtained by converting the carboxyl group of timer acid into an isocyanate group. As the chain extender component used in the production of the polymeric polyol component, various known amine necks can be used. Examples include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and the like. Others have a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. Typical examples include diamine neck and dimer diamine, which is obtained by converting the carboxyl group of dimer acid into an amine group. Furthermore, chain length terminators can also be used. Examples of such chain terminators include dialkylamines such as di-n-butylamine, and alcohols such as ethanol and isopropyl alcohol. The chlorinated polypropylene-modified polyurethane which is the binder of the present invention can be produced by chain-extending prepolymer (I) or a mixture of prepolymer (II) and (Irl). The method for producing the former chlorinated polypropylene-modified polyurethane involves adding a modified chlorinated PP component, a polymer polyol component, and a diisocyanate compound to an isocyanate group/
A prepolymer (■) having isocyanate groups in both components (preferably a free incyanate content of 0.5 to 10%) is produced by carrying out a urethanization reaction under conditions in which the equivalent ratio of hydroxyl groups is 13/1 to 3°0/1. ) and then reacting them with a chain extender and optionally a chain terminator in a suitable solvent. In addition, as a method for producing the latter chlorinated polypropylene-modified polyurethane, the modified chlorinated PP component and the polymer polyol component are each separately treated with a diisocyanate compound so that the isocyanate group/hydroxyl group equivalent ratio is 1.3/1 to 1.3/1.
The prepolymer (Ll) and (II
Ij (preferably M-leaving incyanate content 05-10%
) respectively. These prepolymers (I
A two-step process is used in which a mixture of I') and ([11) is reacted with a chain extender and, depending on the required number, a chain terminator, in a suitable solvent. By manufacturing using the two-step process as described above, the chlorinated polypropylene skeleton and polymer polyol skeleton are uniformly incorporated into the resulting polyurethane molecules, resulting in a chlorinated propylene-modified polyurethane with excellent transparency and solution stability. can get. In the production of the former chlorinated polypropylene-modified polyurethane, the weight ratio of the chlorinated polypropylene component to the polymeric polyol component is approximately 5/95 to 60/40, preferably 10/90 to 50,150. In addition, when producing the latter chlorinated polypropylene-modified polyurethane, the mixing ratio of prepolymer (II) and (river) is approximately 5/95 to 60/40 in order by weight, preferably within the range of 10/90 to 50,150. Ru. In any of the above cases, if the proportion of the chlorinated polypropylene component or prepolymer (II) used is less than 5% by weight, the adhesion to polyolefin will decrease, and if it exceeds 60% by weight, the adhesion to polyester and nylon will decrease. In addition, the conditions for reacting the obtained prepolymer (T) with a chain extender and, if necessary, a chain terminator, may also reduce the properties of the obtained prepolymer (U). ) and (III) with a chain extender and, if necessary, a chain terminator, although there are no particular limitations on the conditions. The amine group in the chain extender is 05-
It is preferably within the range of 1.3 equivalents. When the amine group is less than 0.5 equivalent, drying property, blocking resistance,
If the film strength is not sufficient or is in excess of 1 or 3, the chain extender remains unreacted and the printed matter is likely to have an odor. In the above manufacturing method, the solvents used are usually aromatic solvents such as benzene, toluene, and xylene, which are well known as solvents for printing inks; and alcohols such as methanol, ethanol, isopropanol, and 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 a mixture of two or more. As mentioned above, the number average molecular weight of the polyurethane of the present invention obtained is preferably in the range of 5,000 to 100,000. If the number average molecular weight is less than 500CB,
The drying properties, blocking resistance, film strength, oil resistance, etc. of printing ink using this as a vehicle tend to decrease, and on the other hand, when it exceeds 100,000, the viscosity of the polyurethane resin fi (binder) increases, The gloss of the printing ink tends to decrease.Also, the resin solid content concentration of the polyurethane resin (8 liquids is not particularly limited, but E0
It may be determined as appropriate by considering workability during printing, etc., and is usually 15 to 60% by weight, and the viscosity is 50 to 100,000 cP/2.
It is practically preferable to adjust the temperature within the range of 5°C. Further, in the present invention, a resin compatible with the chlorinated polypropylene-modified polyurethane, which is the main binder component of the present invention, may be used as a subcomponent, if necessary. for example,
Nitrified cotton, chlorinated polyethylene, chlorinated polypropylene,
Chlorinated polyolefins such as chlorinated ethylene/propylene, chlorosulfonated polyolefins, ethylene/vinyl acetate copolymers or their chlorides or chlorosulfonated products, or resins such as maleic acid resins, vinyl chloride/vinyl acetate copolymers, polyurethanes, etc. can give. The thus obtained binder of the present invention contains a colorant, a solvent,
Furthermore, if necessary, a surfactant to improve ink fluidity and ink surface film. The printing ink composition of the present invention can be produced by suitably blending wax and other additives and kneading using a conventional ink production apparatus such as a ball mill, attritor, or sand mill. The amount of the binder of the present invention in the printing ink composition is such that the solid content of the resin is 3 to 20.
Preferably, it is in the range of % by weight.

【Effect of the invention] According to the present invention, a binder for printing ink has excellent adhesion to various plastic films such as polyester, nylon, polyethylene, and polypropylene as printing substrates, and has excellent lamination processing suitability, boiling processing suitability, and retorting processing suitability. and the printing ink composition. 【Example】

The present invention will be described in detail below with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples. Note that parts and percentages are based on weight. Production Example 1 (Synthesis of modified chlorinated PP component) Chlorinated polypropylene (number average molecular weight 300
0 parts of 50% toluene Nagisa droplet liquid with a degree of chlorination of 30%,
32 parts of 2-hydroxyethyl acrylate and 5 parts of t-butyl peroxybenzoate were charged and reacted at 100°C for 4 hours. Further, 1 part of t-butyl peroxybenzoate was added every 2 hours and the mixture was reacted for 4 hours to obtain a resin solution of the modified chlorinated PP component. Resin solid content concentration is 51
%, and the hydroxyl value was 35 KOHmg per 1 g of resin solid content. Production Example 2 Chlorinated polypropylene (
1000 parts of a 40% toluene solution with a number average molecular weight of 5000 and a chloride degree of 40%, 21 parts of 2-hydroxypropyl acrylate, and 3 parts of benzoyl peroxide were charged and reacted at 80°C for 4 hours. Furthermore, 1 part of benzoyl peroxide was added every 2 hours and reacted for 4 hours.
A resin solution of modified chlorinated PP component was obtained. The resin solid content concentration is 41%, and the hydroxyl value is 21 OHm per 1 g of resin solid content.
It was g. Example 1 (Synthesis of chlorinated polypropylene-modified polyurethane) In the same reaction apparatus as in Production Example 1, 588 parts of the modified chlorinated PP component obtained in Production Example 1, adipic acid, and the number obtained from 6-hexanediol were added. Prepare polyester diol l OOC part with an average molecular weight of 2000 and 237 parts of inphorone diisocyanate (NGOloH 1.8)
, free incyanate content 2. ] 8% prepolymer (IA) was obtained. Next, 71.0 parts of isophorone diamine, 14.7 parts of di-n-butylamine, 1334 parts of toluene, 1623 parts of methyl ethyl ketone and 54 parts of isopropyl alcohol were added.
, and reacted with stirring at 50° C. for 3 hours to obtain a chlorinated polypropylene-modified polyurethane resin droplet A having a resin solid concentration of 30% and a number average molecular weight of 29,000. Example 2 1463 parts of the modified chlorinated PP component obtained in Production Example 2, adipic acid and 3-methyl-
Number average molecular weight obtained from 1,5-bentanediol 2
000 polyester diol and 272 parts of isophorone diisocyanate (NC010
H・2.0) was reacted at 100°C for 6 hours under a nitrogen stream to produce a prepolymer with a free isocyanate content of 1.88% (
IB) was obtained. Then, isophorone diamine 95,7
parts, di-n-butylamine 12.8 parts, toluene 111 parts
8 parts, 1981 parts of methyl ethyl ketone, and 660 parts of isopropyl alcohol were added, and the mixture was reacted at 50°C for 3 hours with stirring, resulting in a resin solid content concentration of 30% and a number average molecular weight of 4.
A chlorinated polypropylene-modified polyurethane resin solution B of 0000 was obtained. Example 3 In a reaction apparatus similar to Production Example 1, 1569 parts of the modified chlorinated PP component obtained in Production Example 1, 1000 parts of polycaprolactone diol having a number average molecular weight of 1000, and 416 parts of isophorone diisocyanate (NC010H=1.5) were added. was charged and reacted at 100° C. for 6 hours under a nitrogen stream to obtain a prepolymer (IC) with a free incyanate content of 1.75%. Next, 98.1 parts of isophorone diamine, di-n
- Add 12.0 parts of butylamine, 1557 parts of toluene, 2327 parts of methyl ethyl ketone, and 775 parts of isopropyl alcohol, and react at 50°C for 3 hours with stirring to obtain a chlorination with a resin solid concentration of 30% and a number average molecular weight of 35,000. Polypropylene modified polyurethane resin droplets C
I got it. Example 4 1000 parts of the modified chlorinated PP component obtained in Production Example 1 and 70.6 parts of inphorone diisocyanate were charged into the same reaction apparatus as in Production Example 1 (NGO/DH・20), and 1000 parts of the modified chlorinated PP component obtained in Production Example 1 was charged (NGO/DH・20). The reaction was carried out at .degree. C. for 6 hours to obtain a prepolymer (IIA) with a free isocyanate content of 1.24%. In a separate reactor, 1700 parts of a polyester diol having a number average molecular weight of 2000 obtained from adipic acid and 1,6-hexanediol and 3 parts of isophorone diisocyanate were added.
40 parts (NCO10H=1.8) was charged and reacted at 100°C for 6 hours under a nitrogen stream until the free isocyanate content was 2.
．． 80% of prepolymer (I],] A) was obtained. Next, a mixture consisting of 1070.6 parts of prepolymer 1A) and 2040 parts of prepolymer (IIIA'+2040 parts) and 510 parts of toluene were charged into the river under another counterpressure and into the apparatus.
126-3 parts of inphorondiamine, 25.0 parts of di-n-butylamine, 1772 parts of toluene, 2772 parts of methyl ethyl ketone and 924 parts of isopropyl alcohol were added and reacted at 50°C for 3 hours with stirring until the resin solid concentration was reduced. A chlorinated polypropylene-modified polyurethane resin bath liquid having a number average molecular weight of 30% and a number average molecular weight ffl of 29,000 was obtained. Example 5 1000 parts of the modified chlorinated PP component obtained in Production Example 2 and 34.1 parts of isophorone diisocyanate were charged into the same reaction apparatus as in Production Example 1 (NGOloH 20), and heated to 00°C under a nitrogen stream. The reaction was carried out for 6 hours to obtain a prepolymer (DB) with a free isocyanate content of 0.62%. In another reactor, 684 parts of polyester diol with a number average molecular weight of 2,000 obtained from adipic acid and 3-methyl-1,5-bentanediol and 152 parts of isophorone diisocyanate (NCO10i+・20) were charged, and 100 parts of polyester diol was charged under a nitrogen stream. The reaction was carried out at .degree. C. for 6 hours to obtain a prepolymer (IIIB) having a free isocyanate content of 3.44%. Next, a mixture consisting of 1034.1 parts of prepolymer (IIB) and 836 parts of prepolymer IB) and 209 parts of toluene were further charged into another reactor, and then 65.5 parts of isophoronediamine and 87 parts of di-n-butylamine were added. ,
556 parts of toluene, 1354 parts of methyl ethyl ketone and 451 parts of isopropyl alcohol were added and reacted at 50°C for 3 hours with stirring to obtain chlorinated polypropylene modified polyurethane resin droplets with a resin solid content concentration of 30% and a number average molecular weight of 40,000. Liquid E was obtained. Example 6 In a reaction apparatus similar to Production Example 1, 637 parts of polycaprolactone diol having a number average molecular weight of 1000 and 212 parts of isophorone diisocyanate (NCOlo1=1.5) were added.
1. under a nitrogen stream. The polymer (I
IT(1) was obtained. Next, a mixture of 1070.6 parts of Moeki prepolymer (IIA) and 849 parts of Butshi polymer (IIIC) and 566 parts of toluene were charged into another reactor, and then 75.5 parts of isophorone diamine was added. 8 parts, di-n-butylamine 7
8 parts, 457 parts of toluene, 1513 parts of methyl ethyl ketone
1 part and 504 parts of isopropyl alcohol were added, and the reaction was carried out at 50°C for 3 hours with stirring until the resin solid content concentration was 3.
A chlorinated polypropylene modified polyurethane resin solution F having a number average molecular weight of 0% and a number average molecular weight of 35,000 was obtained. Comparative Example 1 [Synthesis of Comparative Polyurethane] In a reaction apparatus similar to Production Example 1, 1000 parts of a polyester diol with an average molecular weight of 2000 obtained from adipic acid and 1.6-hexanediol and 222 parts of isophorone diisocyanate (NGOloH.2. 0) and heated under nitrogen stream for 10
Reacted at 0°C for 6 hours, free isocyanate content 3.43
After producing % prepolymer, methyl ethyl ketone 8
15 parts were added to form a homogeneous solution of urethane prepolymer. Next, 74.8 parts of inphorondiamine, 15.2 parts of di-n-butylamine, 1093 parts of toluene, 497 parts of methyl ethyl ketone and 65 parts of isopropyl alcohol were added.
A polyurethane resin hot liquid G having a resin solid content concentration of 30% and a number average molecular weight ji of 22,000 was obtained by adding 6 parts of the mixture and reacting at 50° C. for 3 hours. (Preparation of printing ink) Titanium white (rutile type) 30 parts Example 1~
Polyurethane resin solution A obtained in 6 and Comparative Example 1
-G40 parts 1-Luene 15 parts Isopropyl alcohol] A white printing ink was prepared by kneading a mixture of 5 parts in a paint shaker. To 100 parts of the leaked mixture, 35 parts of toluene and 15 parts of isopropyl alcohol were added to adjust the viscosity to prepare seven white printing inks as shown in Table 1. The resulting 7 white printing inks were printed to a thickness of 15 g using a simple gravure printing machine equipped with a gravure plate with a plate depth of 30 um.
Printed on the discharge treated side of a corona discharge treated polypropylene film (OPP), one side of a llum thick polyethylene terephthalate film (PET), and the discharge treated side of a 15 μm thick corona discharge treated nylon film (NY). It was dried at ~50°C to obtain a printed film. (Evaluation of Printed Film) After the above printed matter was left for one day, cellophane tape was attached to the printed surface and the appearance of the printed film was observed and evaluated when the tape was quickly peeled off. The evaluation results are shown in Table 1. 0-111 complete (did not peel off. ○----80% or more of the printed film remained on the film. Δ----50 to 80% of the printed film remained on the film. ×-1 11 Less than 50% of the printed film remained on the film. ■Extrusion lamination rejection agency Regarding OPP for each of the above printed materials, imine-based, PET, N
For Y, use an isocyanate-based anchor coating agent and extrude it into a laminating machine. Therefore, molten polyethylene was laminated, and after 3 days, the sample was
It was cut into mm width and the T-peel strength was determined at boiling point. The evaluation results are shown in Table 1. (3PP Direct Lamination Agency Each of the above OPP printed materials was directly laminated with molten polypropylene using an extrusion laminating machine, and two days later, the peel strength was measured in the same manner as in ■. The evaluation results are shown in Table 1. [Margins below] 1

Claims (1)

[Claims] 1. A chlorinated polypropylene component and a polymer polyol component having an average of 1.5 to 4 hydroxyl groups in the molecule,
Modified chlorinated polypropylene obtained by urethanizing with 1.3 to 3.0 equivalents of a diisocyanate compound per equivalent of these total hydroxyl groups to obtain a prepolymer (I), which is then polymerized using a chain extender. A binder for printing ink characterized by mainly containing polyurethane. 2. A chlorinated polypropylene component having an average of 1.5 to 4 hydroxyl groups in the molecule and a diisocyanate compound in a ratio of 1.3 to 3.0 equivalents of the diisocyanate compound per 1 equivalent of hydroxyl group in the chlorinated polypropylene component. The prepolymer (II) obtained by reacting with the polymeric polyol component and the diisocyanate compound is mixed in a proportion of 1.3 diisocyanate compounds per equivalent of hydroxyl group in the polyol component.
Prepolymer (I) reacted at a ratio of ~3.0 equivalents
A binder for printing ink, characterized in that it mainly contains a chlorinated polypropylene-modified polyurethane obtained by polymerizing a mixture with II) using a chain extender. 3. The binder for printing ink according to claim 1, wherein the weight ratio of the chlorinated polypropylene component and the polymeric polyol component is 5/95 to 60/40 in this order. 4. The binder for printing ink according to claim 1 or 2, wherein the mixing weight ratio of the prepolymer (II) and the prepolymer (III) is 5/95 to 60/40 in this order. 5. Claim 1 or 2, wherein the number average molecular weight of the chlorinated polypropylene-modified polyurethane is 5,000 to 100,000.
Binder for printing ink as described. 6. A printing ink composition for plastics containing the chlorinated polypropylene-modified polyurethane according to claim 1 or 2 as a main binder. 7. The printing ink composition according to claim 6, which is applied to a plastic substrate.