JPH02189375A - Binder for printing ink - Google Patents

Abstract

PURPOSE:To obtain the title binder improved in adhesion to a print, boiling resistance, etc., by using a polyurethane resin obtained by reacting a specified polyester-diol with a diisocyanate compound and a chain extender as the principal component. CONSTITUTION:A polyester-diol of a number-average MW of 500-4000 is obtained by reacting a dibasic acid component comprising at least 50wt.% 20-36C dibasic acid (e.g. dimer acid) and optionally other components with a glycol component. The obtained diol is reacted with a diisocyanate in an amount to give NCO groups in excess of the OH groups of the diol to obtain a prepolymer having an NCO group on each end. This prepolymer is reacted with a chain extender and optionally chain terminator in a solvent to obtain a polyurethane resin of a number-average MW of 5000-10000. This resin is mixed with optionally other resins to obtain the title binder. This binder is mixed with a colorant, a solvent and optionally a surfactant, a wax, and other additives to obtain a printing ink composition.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a binder for printing ink.

(Problems to be solved by conventional technology/invention) In recent years, with the diversification of packaged items and the advancement of packaging technology, four types of plastic films have been developed as packaging materials, and each type is suitable for the packaged items. have been selected and used as appropriate. By the way, when plastic film is used as a packaging material, printing is applied to the plastic film to equip it or to protect its surface.The printing ink used for such printing has good adhesion to these various plastic films. Increasingly, advanced performance is required.

Polyurethane is often used as a printing ink binder for such conventionally used printing inks. In general, printing inks that use polyurethane as a binder have excellent adhesion to polyester and nylon films, but their adhesion to polyethylene and polypropylene films, which are general-purpose films, is insufficient. When printing on or polypropylene film, a two-component reactive ink containing polyurethane and a polyisocyanate compound is used to supplement adhesive strength.

However, two-component reactive inks require a curing agent to be added immediately before printing, making them inconvenient to handle, and they also have the disadvantage of being fairly limited in terms of pot life (pot life). . Therefore, in this field, various research and development are being conducted on polyurethane, which has good adhesion to various plastic films and can be used as a binder for one-component inks that does not require the addition of polyisocyanate compounds. Adhesion has been improved to some extent. However, if the above-mentioned one-component ink is used to print on plastic film, which is used as a packaging base material after food packaging is subjected to boiling sterilization, retort sterilization, etc., the printed matter will not be boil-resistant. resistance, retort resistance (hereinafter referred to as
There is still a problem that the boiling resistance (such as boiling resistance) is still poor.

Therefore, in fields where boiling resistance is required, liquid-based inks are difficult to use, and liquid-reactive inks containing polyisocyanate compounds are still used, despite their drawbacks as mentioned above. Currently, it occupies the mainstream.

The present inventors have solved the problems such as correction, and have achieved a one-component type that provides excellent adhesion, blistering resistance, and blistering properties to various plastic films such as polyester, nylon, polyethylene, and polypropylene as printing substrates. With the aim of providing a binder for printing ink, we have investigated the theory and found that when a polyurethane using a long-chain dibasic acid as the dibasic 11S2 component of polyester diol is used as a binder for printing ink. The inventors discovered that all the problems of the prior art described above can be solved and completed the present invention.

(Means for Solving the Problems) That is, the present invention provides two groups having 20 to 36 carbon atoms'jJ:
: Consists of two groups J, C acid component and glycol component containing at least 50% by weight of acid, and has a number average molecular weight of 5
The present invention relates to a binder for printing ink, characterized in that it mainly contains a polyurethane resin obtained by reacting a polyester diol of 00 to 4000, (1) a diisocyanate compound, and a 030 extender.

In the present invention, as a means for solving the above problems, a polyester diol consisting of two groups containing at least 50% by weight of a dibasic acid having 20 to 36 carbon atoms, an aP11 component, and a glycol component is used. That is, in the present invention, the long-chain dibasic acid has an effect on improving boiling resistance and the like.

Here, the dibasic acid having 20 to 36 carbon atoms refers to two linear or branched saturated or unsaturated long chain groups; 1. ft#, and some of these have cyclo rings and/or
Also included are those having another 7th ring.

In addition, if the number of carbon atoms is less than 20, it is not preferable because the boiling resistance etc. will not be improved.
(manufactured by Henkel Hakusui n) and 22 carbon number Ichangzhen dibasic acid (product name IPS-22, product name fPU-22, Kaifeng Oil @)
gIJ), long chain dibasic acid with 20 carbon atoms (trade name 5L-2
0, wR product name IJL-20, product name 5R-20, product name JI8-20, manufactured by Intermediate Oil Manufacturing Co., Ltd.), long chain dibasic acid with 28 carbon atoms (N product name 5T-2P, manufactured by Intermediate Oil Co., Ltd.) etc. can be mentioned.

Further, among these, it is particularly preferable to use dimer acid in consideration of boiling resistance and the like.

Note that dimer acid usually refers to a polymeric fatty acid obtained by polymerizing unsaturated aliphatic monocarboxylic acids such as linolenic acid and oleic acid, and is generally composed of °, unreacted QtJa form, and the main component. Although it is a mixture consisting of a dimer and other higher-order polymers, if necessary, a dimer acid having a high concentration of dimer by vacuum distillation or the like can also be used.

In addition, the long chain dibasic acid is at least 50% in the dibasic acid component.
It is preferable that the content is less than 50% by weight, and if the content is less than 50% by weight, the boiling resistance etc. will be poor when used as a one-component A1 ink.

It goes without saying that the dibasic acid component of the polyester diol may be 100% long chain dibasic x 4 acids.

In the present invention, 50% by weight of the dibasic acid component contains, in other words, a long chain = ° In addition to the basic acid, the following various known acids generally known as acid components of polyester are used. It can be used in combination as an acid component of polyester diol. For example, adipic acid, maleic acid, fumaric acid,
Dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sepacic acid, and speric acid, or acid anhydrides corresponding to these, etc. It will be done.

In addition, if it is less than 50% by weight and 14%, dibasic acid with 16 carbon atoms (product name 5L-16, product name DI, -16, manufactured by Intermediate Oil Manufacturing), dibasic acid with 12 carbon atoms (product name 5L-12
It is also possible to use intermediate materials such as those manufactured by Yuwa Co., Ltd., etc.

In addition, other glycols forming the long-chain dibasic acid and polyester diol of the present invention include ethylene glycol, diethylene glycol, triethylene glycol, 1.2-propanediol, 1.3-propanediol, 1. 3-butanediol, 1,4-butanediol, neopentyl glycol, bentanediol, 3-methyl-1,5-bentanediol, hexanediol, octanediol, 1,4-butanediol,
Examples include various known saturated and unsaturated glycols such as dipropylene glycol.

In addition, in the present invention, n-butyl glycidyl ether, 2
Alkyl glycidyl ethers such as -ethylhexyl glycidyl ether and monocarboxylic acid glycidyl esters such as persatic acid glycidyl ester can also be used as one of the glycols of the present invention.

Incidentally, up to 5 mol % of the glycol component J- can be substituted with the following various polyols. That is, for example, glycerin, trimethylolpropane, trimethylolethane, 1,2. G-hexanetriol, 1.2.4-butanetriol, sorbitol, pentaerythritol, etc. are examples. It is determined as appropriate in consideration, and is usually within the range of 500 to 4000. If the molecular rhinoceros has a 500-terminus, it tends to have poor printability due to a decrease in solubility;
If it exceeds 00, drying properties and blocking resistance tend to decrease.

Furthermore, within the range that does not deviate from the performance of the above-mentioned polycrethane resin, a part of the polyester diol component can be replaced with low-molecular polyols, and the amount used in the polyol component is usually 20% by weight. The content is preferably 10% by weight or less. Examples of the low-molecular polyols include various low-molecular polyols used in the production of the above-mentioned polymer polyols. The proportion of low molecular weight polyols used is zol! If it exceeds it%, the resulting printing ink composition tends to have poor adhesion to plastic films and poor solubility in diluting solvents, which is not preferable.

Furthermore, within a range that does not deviate from the performance of the polyurethane of the present invention, in addition to the polyester diol described in 1-1, polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran, and dibasic acids may be used. Polyester polyols other than the present invention obtained by condensing glycol components, polyester polyols obtained by ring-opening polymerization of cyclic ester compounds, and others.
Various known polymer polyols commonly used in the production of polyurethane, such as polycarbonate polyols, polybutadiene glycols, and glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, can be used in combination.

In the present invention, as the diisocyanate compound, known diisocyanates of aromatic, aliphatic, or annular type can be used. For example, 1.5-naphthylene diisocyanate, 4.4-diphenylmethane diisocyanate, 4. Diphenyldimethylmethane diisocyanate, 4.4-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-
Di-f isocyanate, hexamethylene diisocyanate, 2.2.4-trimethylhexamethylene diisocyanate, 2.4.4-trimethylhexamethylene diisocyanate, cyclohexane-diisocyanate, 4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate , dicyclohexylmethane-4,4'-diisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane di-f-isocyanate, tetramethylxylylene diisocyanate, and a dimer obtained by converting the carboxyl group of dimer acid into isocyanate t4. Typical examples include diisocyanates.

Furthermore, examples of the chain extender used in the present invention include ethylenediamine, propylenediaminehexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-
4. Diamines such as ediamine, 2-hydroxyethylethylenediamine, 2- and droxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2
- Diamines with a hydroxyl group in the molecule such as hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine, and dimer diamines in which the carboxyl group of dimer acid and the low molecular weight glycol explained in the section on polyester diols above are converted to a 7-mino group, etc. is given as a representative example.

Furthermore, a 3n long terminator can also be added if necessary. Examples of such chain terminators include dialkylamines such as di-n-butylamine, and alcohols such as ethanol and isopropyl alcohol.

Although there are no particular restrictions on the method for producing the polyurethane used in the present invention, for example, a polyester diol component and a diisocyanate compound are reacted under conditions with an excess of isocyanate groups, and a polyester diol having isocyanate groups at both terminals is prepared. A two-step process in which a polymer (preferably 0.5-10% isocyanate content) is prepared 31 and then reacted with a chain extender and optionally a length terminator in a suitable solvent and the polyester diol component, Either one-step method in which a diisocyanate compound, a chain extender, and, if necessary, a chain terminator are reacted all at once in a suitable solvent can be adopted, but a two-step method is preferable because it is easier to obtain a homogeneous polymer solution. It is preferable to adopt the law.

When producing the polyurethane resin used in the present invention by a two-step process, the conditions for reacting the polyester diol component and the diisocyanate compound are not particularly limited, except that the isocyanate groups are in excess; The isocyanate group is 1/1.2 to 1 in electric ratio.
It is preferable to react in a range of /3.Also, there are no particular limitations on the conditions for reacting the obtained prepolymer with a chain extender and, if necessary, a chain terminator, but the prepolymer When the free isocyanate groups at both ends of the polymer are taken as 1 equivalent, the total equivalent of active hydrogen that reacts with the isocyanate groups in the chain extender is 0.5.
-2.0 equivalents, particularly when the active hydrogen-containing group is an amino group, it is preferably in the range of 0.5-1.3 equivalents. If the amount is less than 2.0 equivalents, the drying properties, blocking resistance, and film strength will not be sufficient, and if the amount of active hydrogen is in excess of 2.0 equivalents, the chain extender will remain unreacted, causing an odor to the printed matter. becomes more likely to remain.

In these manufacturing methods, the solvents usually used are:
Benzene, a well-known solvent for printing inks;
Aromatic solvents such as toluene and xylene; methanol, ethanol, -(alcohol solvents such as tuburobanol and n-butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone); If: ethyl acetate, butyl acetate, etc. Esters@solvents are mentioned, and these are used alone or in mixtures of 28i or more.

The number average molecular weight of the polyurethane resin of the present invention obtained as described above is preferably in the range of 5,000 to +00,000. If the number average molecular weight is less than 5,000,
The drying properties, blocking resistance, film strength, oil resistance, etc. of printing inks using this as a vehicle tend to deteriorate.On the other hand, if it exceeds 100QOn, the viscosity of the polyurethane resin solution (binder) increases, and the printing ink The gloss tends to decrease. In addition, the resin solid content concentration of the polyurethane resin solution is not particularly limited, but may be determined appropriately taking into consideration workability during printing, and is usually 15 to 6.
It is practically preferable to adjust the viscosity to 0% by weight and the viscosity to be within the range of 50 to 100,000 cP/25°C.

Further, in the present invention, in addition to the polyurethane which is the main component of the present invention, the following resins may be used as subcomponents as the binder of the present invention. Examples include polyurethanes other than those of the present invention, polyamides, nitrocellulose, polyacrylic esters, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, rosin resins, and ketone resins.

The binder of the present invention is appropriately blended with a colorant, a solvent, and if necessary, a surfactant, wax, and other additives to improve ink fluidity and ink surface film, and is used to produce ordinary inks such as ball mills, attritor sand mills, etc. A printing ink composition can be manufactured by kneading using a manufacturing device. The amount of the binder of the present invention in the printing ink composition is preferably such that the resin solid content of the printing ink composition is 3 to 2%.

less than! ! The present invention will be described in detail with reference to lTi examples, working examples, and comparative examples, but the present invention is not limited to these examples.

Production Example 1 Dimer acid (trade name Versadime 2
88. Prepare 1000 parts of Henkel Hakusui ■a> and 296 parts of 1.6-hexanediol, 9. 200 under bare air flow
Nisgluing was carried out for 24 hours while removing condensation water at °C. After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually reduced using a vacuum pump to complete the reaction. Thus, the hydroxyl value was 57 KOji mg/g, the acid value was 0.4 mg/g, and the number average molecular weight was 2000.
polyester polyol! 0 Production Example 2 172 parts obtained Stirrer, thermometer, water separator and 'E! In a round-bottomed flask equipped with a raw gas introduction tube, add long-chain two-group JAWR <trade name, 5T.
-2P, 1000 parts of intermediary oil (gJJ) and 226 parts of ethylene glycol were charged, and esterification was carried out for 24 hours at 200°C under a stream of 9 atoms while removing condensed water.

After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually reduced using a vacuum pump to complete the reaction.

< t, -c water my4 value 01 MOll mg/g
.

Acid value 0.7 Wolf mg/g, number average molecular weight too
Production Example 3 A long chain dibasic i'le (trade name IPS-
22, manufactured by Okamura Oil Co., Ltd.) and 530 parts of 1,9-nonanediol were charged, and esterification was carried out at 200° C. under a nitrogen stream for 24 hours while removing condensed water.

After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction.

Thus, the hydroxyl value is 35 goa (tag/g, the acid value is 0)
．． 7 1,362 parts of a polyester polyol with a KOH ratio of 3,000 in g/g, number average molecular weight, was obtained.Production Example 4 Into a round bottom flask equipped with a stirrer, a thermometer, a water separator and a nitrogen gas inlet tube, a 8-nm-long incubator was placed. Basic acid (product name SL-, 20
1. ．． 4-Butanediol 3511'! Charge S and heat under nitrogen stream for 2 hours.
Esterification was carried out at 00° C. for 24 hours while removing condensed water.

After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction.

Thus, the water lv2 base value is 54 and the O)l mg/g% acid value is 0.
．． 2 KOJI-gig, obtained 1183 parts of polyester polyol with a number average molecular weight of 2000.0 FJ Production Example 5 A long chain dibasic acid ( Mix 600 parts of product name 5L-20 (manufactured by Intermediate Oil Co., Ltd.), 400 parts of adipic acid, and 335 parts of ethylene glycol, and add 200 parts of ethylene glycol under a nitrogen stream.
Esterification was carried out for 24 hours while removing water of condensation at °C. After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction. Thus, hydroxyl value 56KO1l mg/g% acid value 0
．． 011 parts g/g in 3, 1115 parts of a polyester polyol with number average molecular jj 2000 was obtained 1'! lJ Preparation Example 6 Into a round bottom flask equipped with a stirrer, thermometer, water separator and nitrogen gas inlet tube, 1000 parts of adipine fi and 1
．． 950 parts of 6-hexanediol was charged, and esterification was carried out at 200° C. under a nitrogen stream for 24 hours while removing condensed water. After confirming that the acid value of the polyester was 2 or less, the vacuum pump was used to gradually complete the ゛(fiber-forming reaction).
/g, acid (1i0.2 KOII mg/g, number average molecule;, Hooo's polyester polyol 1618
Production Example 7 A long chain dibasic acid (trade name St, -12
1,000 parts (manufactured by Intermediate Oil Co., Ltd.) and 802 parts of 1.9-nonanediol were charged, and esterification was carried out at 200° C. under a nitrogen stream for 24 hours while removing condensed water.

After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction.

Thus, the hydroxyl value of KOII Bag is 33, and the acid value is 0.
5 was added with 1 5 +i 3 parts of a polyester polyol having an average molecular weight of 3,000 and an oil mg/g.

Production Example 8 A long chain dibasic acid (trade name St, -16
, intermediate oil ■%J) 1000 parts and ethylene glycol 3
10 parts were charged, and esterification was carried out at 200° C. under a nitrogen stream for 24 hours while removing condensed water.

After confirming that the acid value of the polyester was 2 or less, a portion of the vacancy was gradually removed using a vacuum pump to complete the reaction. In this way, the hydroxyl value is 115 and the acid value is 0.
4 KOII I! 1g/X, ? j average molecule U'(1
000 (7) 1125 parts of polyester polyol were obtained.Production Example 9 Into a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, the polyester polyol 10 obtained in Production Example 1 was placed.
00 parts of isophorone diisocyanate and 222 parts of isophorone diisocyanate were reacted for 6 hours under a 9 R gas flow at too high a temperature to produce 5 prepolymers containing free isocyanate, and then 815 parts of methyl ethyl ketone was added to form a urethane prepolymer. A homogeneous solution of the polymer was obtained.

Next, 2037 parts of the urethane prepolymer solution was added to a mixture consisting of 77.5 parts of isophoronediamine, 8.4 parts of di-n-butylamine, 1220 parts of methyl ethyl ketone, and 1017 parts of isopropyl alcohol.

Then, the mixture was reacted at 50°C for 3 hours. The thus obtained polyurethane resin IFI solution (hereinafter referred to as resin solution A) has a resin solid content concentration of 30% and a viscosity of 580 cP/2.
! It was i°C. Further, the number average molecular weight of the polyurethane resin was 38,000.

Production Example 10 Polyester polyol 1 obtained in Production Example 2 was placed in a round bottom flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube.
000 parts of isophorone diisocyanate and 333 parts of isophorone diisocyanate were charged and reacted for 16 hours under a stream of bare air at 13.02% of isocyanate. A homogeneous solution of the polymer was obtained.

Next, 2148 parts of the urethane prepolymer solution was added to a mixture consisting of 75.4 parts of inphorondiamine, 9.1 parts of di-n-butylamine, 1390 parts of methyl ethyl ketone, and 1103 parts of isopropyl alcohol, and then reacted at 50°C for 3 hours. I let it happen. The thus obtained polyurethane resin solution (hereinafter referred to as resin solution B) had a resin solid content concentration of 30% and a viscosity of 470 cP/25°C. In addition, the number average molecular weight of polyurethane resin is 34
It was 000.

Production Example 11 Polyester polyol 10 obtained in Production Example 3 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube.
00 parts and -tetramethylxylylene diisocyanate 2
03 parts was charged and reacted at 130°C for 6 hours under a nitrogen stream, T1t! ! After producing a prepolymer containing 3.38% isocyanate, 815 parts of methyl ethyl ketone was added to make a homogeneous solution of urethane prepolymer. Next, 76.8 parts of isophorone diamine, 8.3 PIS of di-n-butylamine, The urethane prepolymer solution 20181'J5 was added to a mixture consisting of 1,189 parts of methyl ethyl ketone and 1,002 parts of isopropyl alcohol, and then reacted at 50° C. for 3 hours. The thus obtained polyurethane resin +111 solution (hereinafter referred to as resin solution C) has a resin solid content concentration of 30% and a viscosity of 780 cP.
The temperature was 725°C. Further, the number average molecular weight of the polyurethane resin was 41,000.

Production Example 12 Polyester polyol 10 obtained in Production Example 4 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube.
00 parts of isophorone diisocyanate and 222 parts of isophorone diisocyanate were reacted at 100°C for 6 hours under a nitrogen λ5 stream to produce a prepolymer with an interstitial isocyanate content of 13.38%, and then 815 parts of methyl ethyl ketone was added to form a homogeneous solution of urethane prepolymer. did.

Next, 2037 parts of the urethane prepolymer solution was added to a mixture consisting of 78.1 parts of isophoronediamine, 8.4 parts of di-n-butylamine, 1220 parts of methyl ethyl ketone, and 1018 parts of isopropyl alcohol, and then reacted at 50°C for 3 hours. Ta. The thus obtained polyurethane resin solution (hereinafter referred to as resin solution) had a resin solid content concentration of 30% and a viscosity of 720 cP and 725°C. In addition, the number average molecular weight of polyurethane resin is 400
It was 00.

Production Example 13 In a round bottom flask equipped with a stirrer, thermometer and nitrogen gas inlet tube,! 1,000 parts of the polyester polyol obtained in IJ Preparation Example 5 and 222 parts of isophorone diisocyanate were added and reacted at 100°C for 6 hours under a nitrogen stream to produce a prepolymer with a free heel isocyanate content of 3.40%, followed by methyl ethyl ketone 815. 1 part to make a homogeneous solution of urethane prepolymer.

Next, 2037 parts of the fermented urethane prepolymer solution was added to a mixture consisting of 78.6 parts of isophorone diamine, 8.4 parts of di-rope tylamine, 21221 parts of methyl ethyl keto and 1018 parts of isopropyl alcohol, and the mixture was heated at 50°C for 3 hours. On the contrary; let it happen. The polyurethane resin temperature Fi (hereinafter referred to as resin solution E) obtained in this way is:
Resin solid content concentration is 30%, viscosity is 1100 cP 72
The temperature was 5°C. Further, the number average molecular weight of the polyurethane resin was 39,000.

Production Example 14 Polyester polyol 60 obtained in Production Example 1 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube.
0 parts Polyester polyol obtained in Production Example 6 40
0 parts and 222 parts of isophorone diisocyanate were charged and reacted at 100°C for 6 hours under a nitrogen stream to produce a prepolymer with a free isocyanate content of 3.36%.
815 parts of methyl ethyl ketone was added to make a homogeneous solution of urethane prepolymer.
6.4 parts, di-n-butylamine 10.1 parts, methyl ethyl ketone 1221 parts and isopropyl alcohol 10
Add 2037 parts of the urethane prepolymer solution to the 18 parts mixture, and then! The reaction was carried out at 10°C for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as
The resin solution F) had a resin solid concentration of 30% and a viscosity of 720 cP and 725°C. Further, the number average molecular weight of the polyurethane resin was: 18,000.

Production Example 15 Polyester polyol 10 obtained in Production Example 6 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube.
00 parts and 222 parts of isophorone diisocyanate were charged and reacted at 100°C for 6 hours under a nitrogen stream to produce a prepolymer with a free isocyanate content of 3.36%. Then, 815 parts of methyl ethyl ketone was added to form a uniform urethane prepolymer. Next, 2037 parts of the urethane prepolymer solution was added to a mixture consisting of 75.3 parts of isophoronediamine, 11.8 parts of di-n-butylamine, 1221 parts of methyl ethyl ketone, and 1018 parts of isopropyl alcohol, and the mixture was heated at 50°C. The thus obtained polyurethane resin solution (hereinafter referred to as resin solution G), which was reacted for 3 hours, had a resin solid content concentration of 30% and a viscosity of 1800 cP and 725°C. Further, the number average molecule r11 of the polyurethane resin was 24100G.

Production Example 16 Polyester polyol 10 obtained in Production Example 7 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube.
00 parts and 203 parts of -tetramethylxylylene diisocyanate were charged and reacted for 6 hours at 130°C under a nitrogen stream to produce a TttR- (prepolymer with a socyanate content of 3.37%), and then 815 parts of methyl ethyl ketone was added to form a urethane. Then, 2018 parts of the urethane prepolymer solution was added to a mixture consisting of 76.5 parts of isophorone diamine, 8.3 parts of di-n-butylamine, 1188 parts of methyl ethyl ketone, and 1002 parts of isopropyl alcohol, which was made into a homogeneous solution of the prebolimer. then 5
The reaction was carried out at 0°C for 3 hours. The thus obtained polyurethane J31i solution (hereinafter referred to as JF?solution H) has a resin solid content concentration of 30% and a viscosity of +100 cP 725
It was ℃. Further, the number average molecular weight of the polyurethane tree IFm was 38,000.

Production Example 17 The polyester polyol obtained in Production Example 8 was placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
00 parts of isophorone diisocyanate and 333 parts of isophorone diisocyanate were charged and reacted for 6 hours at 100°C under a nitrogen stream to produce a prepolymer with a free isocyanate ratio of 1:+, oo%. Then, 815 parts of methyl ethyl ketone was added to form a homogeneous solution of urethane prepolymer. Then, 74.9 parts of isophorone diamine, 9.1 parts of di-n-butylamine, 1389 parts of methyl ethyl ketone and 1 part of isopropyl alcohol were added.
2148 parts of the urethane prepolymer solution was added to the mixture consisting of 102 parts, and the mixture was reacted at 50° C. for 3 hours. The thus obtained polyurethane resin solution (hereinafter referred to as resin solution I) had a resin solid content concentration of 30% and a viscosity of +400 cP and 725°C. The number average molecular weight of the polyurethane resin was 40,000.

Examples 1-6 and Comparative Examples 1-4 Titanium white (rutile type) 30 parts Production example 9-! A mixture of the polyurethane resin solution obtained in step 7, 50 parts toluene, 10 parts isopropyl alcohol, and 10 parts was kneaded in a paint shaker to obtain white printing inks 'A' and 6. To 100 parts of the resulting mixture, 35 parts of toluene and 15 parts of isopropyl alcohol were added to adjust the viscosity to prepare nine white printing inks as shown in Table 1.

The white printing ink of Comparative Example 4 was obtained by adding 2 parts of isophorone diisocyanate to the one obtained in Comparative Example 1 to make a two-component printing ink.

The obtained 10 white printing inks were printed on a corona discharge treated nylon film (NY) with a thickness of 15μ by using a simple gravure printing machine equipped with a gravure plate with a plate depth of 30μ. A printed film was obtained by printing on one side of polyethylene terephthalate (PET) having a thickness of IIμ and the L-electrotreated side and drying at 40 to 50°C.

Then, on the printing surface of the obtained printing film, the solid content was 2
A laminate film was obtained by drying a 5% polyurethane adhesive at a coating amount of 3 g/g on a cloth and dry laminating a 60 μm polyethylene film using a laminator. The laminate strength (adhesive force) and boilability at 100° C. of the laminate film thus obtained were evaluated. The evaluation results are shown in Table 1.

(1) Evaluation of change in appearance of film The change in appearance of the laminated film was observed after boiling it at 100° C. for 30 minutes.

0---------No abnormality with the film.

Δ---A small portion of the film is delaminated or a small amount of blistering occurs.

X---------A part of the film is delaminated or blistering occurs.

(2) Changes due to lamination strength (adhesive strength) After boiling the laminated film at 100℃ for 30 minutes,
The sample was cut into s width, and the T-peel strength (unit: g/J5 mm) was measured using a peel tester at a speed of 300 mm/min and compared with the strength before boiling.

The one-component printing ink using the printing ink binder of the present invention has excellent tackiness and resistance to printing on various plastic films such as polyester, nylon film, polyethylene, and polypropylene. It has the effect of exhibiting boiling properties.

Procedure Amendment Old (voluntary) February 3, 1999 1 Display of the case 1999 Patent Application No. 10681 2 Name of the invention Binder for printing ink 3 Person making the amendment Relationship to the case Patent applicant 1999 February 13th, Address change due to implementation of residence indication 5
Target of amendment (1) The statement ``Detailed Description of the Invention J, Section 6 Contents of amendment (1) Item 7, line 18 of the specification includes category r.'' can be cited as category r. ” he corrected.

(2) "2-ethylhexyl glycidyl ether, etc. esters" in section 7, line 20 of the specification to section 8, line 3 of the specification is replaced with "2-ethylhexyl glycidyl ether, etc." , monoglycidyl ethers such as 2-methyloctylglycidyl ether, allylglycidyl ether, phenylglycidyl ether, phenylphenol glycidyl ether, alkylphenylglycidyl ether,
monoglycidyl esters such as persatic acid glycidyl ester, rosin glycidyl ester, glycidyl methacrylate, monooxides such as octylene oxide, styrene oxide, cyclohexene vinyl monooxide, α-pinene oxide, olefin oxide, diterpene oxide, etc.” .

(3) In Section 11, Lines 12-13 of the specification, "diamines" is corrected to "polyamines."

(4) In paragraph 30, line 11 of the specification, add a new line after "compared to previous strength," and add the following sentence.

"Production Example 18 Dimer acid (trade name Versadime 288
, manufactured by Henkel Hakusui ■) and 1000 parts of persatic acid glycidyl ester (trade name Cardura E% Shell Chemical ■
Esterification was carried out at 200° C. under a nitrogen stream for 16 hours while removing condensed water. After confirming that the acid value of the polyester was 2 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction. Thus, the hydroxyl value was 56,110 parts mg/g, and the acid value was 0.2 KOH.
A polyester polyol with a number average molecular weight of 2,000 and r460eB was obtained.

Production Example 19 In a round bottom flask equipped with a stirrer, a thermometer, a water separator, and a nitrogen gas inlet tube, 1000 parts of a long chain dibasic acid (trade name IPS-22, manufactured by Intermediate Oil Co., Ltd.) and 2-ethylhexyl were added. Add 650 parts of glycidyl ether and heat at 200°C under nitrogen stream.
Esterification was carried out for 20 hours while removing water of condensation.

After confirming that the acid value of the polyester has become 2 or less,
The degree of vacuum was gradually increased using a vacuum pump to complete the reaction. Thus, the hydroxyl value is 53, the KOH value is g/g, and the acid value is 0.3.
1,460 parts of polyester polyol having a number average molecular weight of 2,000 onwg/g was added.

Production Example 20 1000 parts of the polyester polyol obtained in Production Example 18 and 222 parts of isophorone diisocyanate were placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, and the mixture was reacted at 100°C for 6 hours under a nitrogen stream. After producing a prepolymer with a free isocyanate content of 3.35%, 815 parts of methyl ethyl ketone was added to form a homogeneous solution of urethane prepolymer. 2,037 parts of the urethane prepolymer solution were added to a mixture consisting of 1,017 parts of isopropyl alcohol and 1,017 parts of isopropyl alcohol, and then reacted at 50° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as resin solution J) had a resin solid content concentration of 30% and a viscosity of 470 cP/25°C. Further, the number average molecular weight of the polyurethane resin was 37,000.

Production Example 21 1000 parts of the polyester polyol obtained in Production Example 19 and 222 parts of isophorone diisocyanate were placed in a round bottom flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, and the mixture was reacted at 100°C for 6 hours under a nitrogen stream. After producing a prepolymer with a free incyanate content of 3.36%, 815 parts of methyl ethyl ketone was added to make a homogeneous solution of urethane prepolymer. 2,037 parts of the urethane prepolymer solution was added to a mixture of 12201 and 10.7 parts of isopropyl alcohol, and the mixture was reacted at 50° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as
The resin solution had a resin solid content concentration of 30% and a viscosity of 420 cP/25°C. Further, the number average molecular weight of the polyurethane resin was 39,000.

Example 7.8 Titanium white (rutile type) 30 parts Polyurethane resin solution obtained in Production Example 18.19 50 parts Toluene
10 parts isopropyl alcohol
A mixture having a composition of 10 parts was ground in a paint shaker to prepare a white printing ink. To 100 parts of the resulting mixture, 35 parts of toluene and 15 parts of isopropyl alcohol were added to adjust the viscosity to 31. J2
Two white printing inks were prepared as shown in the table. The obtained two white printing inks were evaluated in the same manner as in Examples 1 to 6. The evaluation results are shown in Table 2.'' (5) Add the following table on a new line after Table 1 in Item 31 of the specification.

Claims (1)

[Claims] 1. (a) At least 5 dibasic acids having 20 to 36 carbon atoms
Mainly a polyurethane resin obtained by reacting a polyester diol consisting of a dibasic acid component and a glycol component containing 0% by weight and having a number average molecular weight of 500 to 4000, (b) a diisocyanate compound, and (c) a chain extender. A binder for printing ink characterized by containing.