JPH0616762A - Urethane resin-modified polyethyleneimine and method for producing the same - Google Patents

Abstract

PURPOSE:To obtain a polyethyleneimine modified with urethane resin having increased adhesion-promoting function and improved water-resistance, applicable to the use necessitating retort sterilization, etc., and useful for adhesive, etc., by reacting a linear polyurethane monoisocyanate with a polyethyleneimine. CONSTITUTION:A polymeric diol (e.g. polyester diol) is made to react with an organic diisocyanate (e.g. 1,6-hexamethylene diisocyanate) and optionally a chain extender (e.g. ethylene glycol) using the isocyanate in excess to obtain a urethane polymer having isocyanate group on the terminal. A part of the terminal isocyanate group is reacted with a chain terminator (e.g. methyl alcohol) to obtain a chain polyurethane monoisocyanate. The product is added to a polyethyleneimine and the remaining terminal isocyanate groups are made to react with the polyethyleneimine to obtain the urethane resin-modified polyethyleneimine useful e.g. as an additive to a printing ink, etc., to improve the adhesiveness of the ink to a plastic film, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane resin-modified polyethyleneimine and a method for producing the same, and more specifically, a urethane resin-modified polyethyleneimine useful as an additive to a printing ink or the like which improves adhesion to a plastic film and the like. The manufacturing method is related.

[0002]

2. Description of the Related Art Polyethyleneimine has been conventionally applied to the adhesive industry field, and has been used for anchoring agents for laminating various plastic films and foils, adhesive compositions, and improving paint adhesion. However, since polyethyleneimine is extremely hydrophilic, the adhesive strength is significantly reduced when it comes into contact with water, and it is not suitable for applications requiring water resistance, especially hot water resistance.

[0003]

DISCLOSURE OF THE INVENTION The present invention is a modified type that can more effectively bring out the adhesion promoting function of polyethyleneimine and can also be applied to applications requiring water resistance of the adhering surface, and by extension, boil sterilization or retort sterilization. It is intended to provide polyethyleneimine.

[0004]

The present inventors have completed the present invention as a result of earnest researches for solving the above problems.

That is, the present invention relates to a urethane resin-modified polyethyleneimine obtained by reacting a linear polyurethane monoisocyanate with polyethyleneimine, and a method for producing the same.

The linear polyurethane monoisocyanate used in the present invention may include those having various structures.
For example, a high molecular diol, an organic diisocyanate and, if necessary, a chain extender are reacted in an excess molar ratio of isocyanate to give a urethane prepolymer having an isocyanate group at the terminal, and a part of the terminal isocyanate group is reacted with a chain terminator. Includes what you get.

The polymer diol used for producing the polyurethane monoisocyanate used in the present invention includes polyester diols such as dicarboxylic acids (adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, Phthalic acid) and glycols (ethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol,
1,6-hexanediol, 1,8-octamethylenediol, neopentyl glycol, bishydroxymethylcyclohexane, bishydroxyethylbenzene, alkyl dialkanolamine, etc.) obtained by polycondensation, for example, polyethylene adipate, poly Butylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate; polylactone diols by ring-opening polymerization of lactones such as polycaprolactone diol, polyvalerolactone diol, and polyether polyols such as polyether polyols [low molecular weight glycols (ethylene glycol, propylene Alkylene oxide of glycol, 1,4-butanediol, etc. (Alkylene oxide having 2 to 4 carbon atoms such as ethylene Kishido, propylene oxide and butylene oxide) adducts and ring-opening polymerization of the alkylene oxide] Specifically polyethylene glycol,
Examples include polypropylene glycol and polytetramethylene ether glycol and mixtures of two or more thereof. Of these, polyester diol is particularly preferable. The average molecular weight of the polymeric diol (as measured by the hydroxyl value) is usually 500 to 40,000, preferably 800 to 800.
It is 0.

As the organic diisocyanate, aliphatic diisocyanates (1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, ethylene glycol, propylene glycol, and other low-molecular-weight glycols and the above aliphatic diisocyanates are used. Prepolymer, etc.);
Alicyclic diisocyanates (isophorone diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, methylcyclohexylene diisocyanate, isopropylidene dicyclohexyl 4,4'-diisocyanate, prepolymers of low molecular glycols and the alicyclic diisocyanates, etc. ); Aromatic diisocyanates (4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, prepolymers of low-molecular glycols and the aromatic diisocyanates); and two or more thereof. A mixture of Of these, preferred are aliphatic diisocyanates and alicyclic diisocyanates and mixtures thereof.

Examples of chain extenders include low molecular weight glycols (ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, etc., aliphatic diamine (ethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, etc.), alicyclic diamine (isophoronediamine, dicyclohexylmethane-4, etc.) 4'-diamine, isopropylidenedicyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, etc.) and mixtures of two or more thereof. Of these, preferred are low molecular weight glycols, alicyclic diamines and mixtures of two or more thereof.

As the chain terminator, monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol and iso-butyl alcohol; monoethylamine, n-propylamine, diethylamine, Gee n
Examples include monoamines such as -propylamine and di-n-butylamine; hydroxyl monoamines such as monoethanolamine and diethanolamine.

The molar ratio of the polymeric diol and the chain extender is usually
It is 1: 0.3 to 1: 8, preferably 1: 0.5 to 1: 6.

NCO and active hydrogen-containing groups (OH, NH ₂ ,
The ratio of (NH, etc.) is usually 1: 0.8 to 1: 0.98.

The polyurethane monoisocyanate used for producing the urethane resin-modified polyethyleneimine of the present invention can be produced by the following method. For example, an organic diisocyanate and a high molecular weight diol are reacted at an excess molar ratio of an isocyanate group to form a urethane prepolymer having a terminal isocyanate group, the urethane prepolymer is diluted with a solvent to obtain a solvent solution of the urethane prepolymer, and then a chain A method in which a chain terminator is added after elongation with an elongating agent, or a method in which an organic diisocyanate, a polymeric diol, and a chain elongating agent are reacted in a solvent solution in a single step and then a chain terminator is added You can It is also possible to add a part of the chain extender (for example, low molecular weight glycol) at the time of producing the urethane prepolymer and to extend it with the rest of the chain extender (for example, diamine), and then add a chain terminator.

The resin thus obtained may contain a diisocyanate and a polyurethane resin having no isocyanate group in addition to polyurethane monoisocyanate. The diisocyanate is gelled by the reaction with polyethyleneimine in the next step. Therefore, it is necessary to add an amount of the chain terminator that does not substantially contain it. Polyurethane resin containing no isocyanate group does not participate in the reaction with polyethyleneimine but serves as a suitable binder component in the intended use of the present invention, and thus may be contained.

When a solvent is used, examples of the solvent used include alcohols such as ethanol, isopropanol and n-butyl alcohol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromas such as toluene. Group hydrocarbons; esters such as ethyl acetate, butyl acetate and the like, and mixtures of two or more thereof, and preferably isopropanol, from the viewpoint of solubility and economy.
It is n-butyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene and a mixture of two or more thereof.

However, when alcohol is contained as a solvent, it is necessary to shift to the reaction with polyethyleneimine in the next step before it reacts with the isocyanate group in the polyurethane monoisocyanate.

A catalyst may be used in the reaction of polyurethane. Examples of such a catalyst include tertiary amine-based catalysts such as triethylamine and dimethylaniline, and metal-based catalysts such as tin and zinc.

The molecular weight of the polyurethane monoisocyanate thus obtained is usually 4,000 to 80,000, preferably 6,000 to 60,000.

The polyethyleneimine used in the production of the urethane resin-modified polyethyleneimine of the present invention is obtained by the polymerization of ethyleneimine and has a molecular weight of about 300 to 100,000. Preferably, it has a molecular weight of about 600 to 30,000. If the molecular weight is lower than this range, the adhesion promoting function is not sufficient. On the other hand, if the molecular weight exceeds this range, gelation tends to occur when modified with a urethane resin, which is not suitable. Examples of commercially available products include Epomin SP-006, SP-012, SP-018, SP-, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.
There are 200 etc., and they can be easily obtained.

In the production of the urethane resin-modified polyethyleneimine of the present invention, the reaction between polyurethane monoisocyanate and polyethyleneimine can be carried out by the following method. For example, a solvent solution of polyethyleneimine may be prepared, and the above-mentioned polyurethane monoisocyanate may be gradually added thereto at a temperature of room temperature to 60 ° C while stirring. As the solvent used for the solvent solution of polyethyleneimine, for example, lower alcohols such as methanol, ethanol and isopropanol are suitable, but ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran within a range that does not impair the solubility. An ester such as ethyl acetate or butyl acetate, and a mixture of two or more kinds thereof may be used. The resin concentration of the solvent solution of polyethyleneimine is not particularly limited, but in order to avoid the risk of gelation, it is preferably 2 to 50% by weight, more preferably 3 to 20% by weight.

In the above-mentioned polyurethane resin-modified polyethyleneimine, the ratio of polyethyleneimine to polyurethane resin is 1/9 to 9/1, preferably 2/9 by weight.
It is 8 to 8/2. The ratio of polyethyleneimine is 10%
If it is less than 90%, gelation is likely to occur and production is difficult.
If it exceeds the above range, the effect of the present invention due to the modification of the polyurethane resin cannot be obtained.

[0022]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be described more specifically, but the present invention is not limited thereto.

Example 1 (Synthesis of Polyurethane Monoisocyanate) A round bottom flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube was subjected to an esterification reaction of 1,4-butanediol with adipic acid having an average molecular weight of 2000. 2000 parts (1 mol) of the obtained polyester diol was charged, and the temperature was raised to 70 ° C. with stirring.

At the same temperature, 444 parts (2 mol) of isophorone diisocyanate was added and reacted for 7 hours while flowing nitrogen gas, and then cooled to 40 ° C while adding methyl ethyl ketone and 3010 parts of ethyl acetate. And
It was dissolved uniformly. 136 parts (0.8 mol) of isophoronediamine was added thereto and reacted at 40 ° C. for 5 hours at the same temperature to obtain a urethane prepolymer having a nonvolatile content of 30%.

Here, 10.2 parts (0.14 mol) of diethylamine
And 23.8 parts of ethyl acetate were added, and the mixture was further reacted for 2 hours to obtain a polyurethane monoisocyanate solution having a nonvolatile content of 30%.

(Synthesis of urethane resin-modified polyethyleneimine) A reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube was charged with Epomin SP-200 [polyethyleneimine manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., molecular weight about 1000].
0] 12.3% solution (in a mixed solvent of ethyl acetate and isopropyl alcohol 9: 1) 56.7 parts was prepared, and the above-mentioned non-volatile content 30% polyurethane monoisocyanate solution
Add 10 parts (polyethyleneimine / polyurethane =
7/3), react at 40 ℃ for 2 hours, non-volatile content 15.0%,
A urethane resin-modified polyethyleneimine solution having a polyethyleneimine content of 10.5% was obtained.

Example 2 (Synthesis of Polyurethane Monoisocyanate) Example 1 was prepared by adding 11.0 parts (0.15 mol) of diethylamine and 25.7 parts of ethyl acetate to the same amount and the same amount of urethane prepolymer solution as that used in Example 1. A polyurethane monoisocyanate solution having a nonvolatile content of 30% was obtained in the same manner as in.

(Synthesis of Polyurethane Imine Modified with Urethane Resin) Epomin SP-200 1 was prepared in the same manner as in Example 1.
Prepare 50 parts of a 0% solution, add 16.7 parts of the above-mentioned polyurethane monoisocyanate solution with a nonvolatile content of 30% (polyethyleneimine / polyurethane = 5/5), and add 40 ° C.
The reaction was carried out for 2 hours to obtain a solution of urethane resin-modified polyethyleneimine having a nonvolatile content of 15.0% and a polyethyleneimine content of 7.5%.

Example 3 (Synthesis of Polyurethane Monoisocyanate) Example 1 was prepared by adding 11.7 parts (0.16 mol) of diethylamine and 27.3 parts of ethyl acetate to the same amount and the same amount of urethane prepolymer solution as that used in Example 1. A polyurethane monoisocyanate solution having a nonvolatile content of 30% was obtained in the same manner as in.

(Synthesis of Urethane Resin Modified Polyethyleneimine) In the same manner as in Example 1, 5 of Epomin SP-200 was prepared.
% Solution 40 parts was prepared, and 26.7 parts of the above-mentioned polyurethane monoisocyanate solution with a non-volatile content of 30% was added (polyethyleneimine / polyurethane = 2/8) at 40 ° C.
After reacting for a period of time, a solution of urethane resin-modified polyethyleneimine having a nonvolatile content of 15.0% and a polyethyleneimine content of 3.0% was obtained.

Test Examples and Comparative Examples Each urethane resin-modified polyethyleneimine obtained in Examples 1 to 3 and the following polyurethane resin for inks,
The printing ink base and the solvent were mixed to prepare the inks shown in Table 1. Each of the inks shown in Table 1 has a pigment / urethane resin ratio of 12.5 / 9 in terms of solid content and is formulated so that the nonvolatile content of the ink is 34.7%. In addition, Test Examples 1 to 3 and Comparative Example 2 were prepared so that the content of polyethyleneimine was 0.9% in the solid content of the ink, and that of Test Examples 4 to 6 and Comparative Example 3 was 1.8%.

Polyester film (abbreviated as PET), nylon film (abbreviated as NY) and biaxially oriented polypropylene film (abbreviated as OPP) are used for these inks.
And the adhesiveness of each ink film in the normal state and the adhesiveness after immersion in water for NY were also tested. The comparative examples were those in which no polyethyleneimine component was added and those in which unmodified polyethyleneimine was added, and the same test was conducted.

The test results are shown in Table 1 together with the ink formulation.

(Synthesis of Polyurethane Resin for Ink) In a 2 liter round bottom flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 319 g of polycaprolactone diol having an average molecular weight of 2000 was charged and stirred. The temperature was raised to ° C.

At the same temperature, 71 g of isophorone diisocyanate was added and the reaction was carried out for 7 hours while flowing nitrogen gas, and then methyl ethyl ketone and ethyl acetate were added.
While adding g each, the mixture was cooled to 40 ° C and uniformly dissolved.

24 g of isophoronediamine and 290 g of isopropyl alcohol were added to the prepolymer thus obtained.
Is added, and the mixture is reacted at the same temperature of 40 ° C for 5 hours.
A colorless transparent polyurethane resin solution having a Gardner viscosity of YZ of 30% at 25 ° C. was obtained.

(Preparation of Printing Ink Base) 50 parts of the polyurethane resin solution for ink obtained above was diluted with 10 parts of methyl ethyl ketone, 10 parts of ethyl acetate and 5 parts of isopropyl alcohol, and then 25 parts of titanium oxide was added to the ball mill. The mixture was kneaded for 24 hours to obtain a urethane printing ink base.

(Adhesion test) Each film was coated with each ink using a draw down rod # 18, the solvent was volatilized, and the pressure was heated to 50 ° C. for 80 k.
The same film was laminated on the ink surface at a pressure of g / cm ² and laminated, and then aged at 40 ° C for 36 hours.

This is cut into a tape having a width of 15 mm,
Using Tensilon RTM-25 manufactured by Orientec Co., Ltd., the peel strength by T-type peeling at a speed of 300 mm / min (g
/ 15 mm). The measurement was carried out for all the normal ones, and the NY laminate was also immersed for 5 hours in water.

[0040]

[Table 1]

[0041]

The urethane resin-modified polyethyleneimine according to the present invention can be stably produced without gelation according to the method of the present invention.

The urethane resin-modified polyethyleneimine of the present invention can more effectively bring out the adhesion promoting function of polyethyleneimine, and when added to urethane-based printing ink, the adhesiveness of the ink film to various plastic films is remarkably improved. This also allows the water resistance of the adhesive surface to be maintained at a high level. Further, the urethane resin-modified polyethyleneimine of the present invention is useful in addition to an additive for a printing ink, an anchor agent for laminating various plastic films and foils, an adhesive composition, and improvement of paint adhesion.

Claims (9)

[Claims] 1. A urethane resin-modified polyethyleneimine obtained by reacting a linear polyurethane monoisocyanate with polyethyleneimine. 2. Polyethyleneimine having a molecular weight of 300 to
The urethane resin-modified polyethyleneimine according to claim 1, which is 100,000. 3. The urethane resin-modified polyethyleneimine according to claim 1, wherein the ratio of polyethyleneimine to urethane resin is in the range of 1/9 to 9/1 on a weight basis. 4. A method for producing a urethane resin-modified polyethyleneimine, which comprises reacting linear polyurethane monoisocyanate with polyethyleneimine. 5. Polyethyleneimine having a molecular weight of 300 to
It is 100,000, The manufacturing method of the urethane resin modified polyethyleneimine of Claim 4. 6. The method for producing a urethane resin-modified polyethyleneimine according to claim 4, wherein the ratio of polyethyleneimine to urethane resin is in the range of 1/9 to 9/1 on a weight basis. 7. A high-molecular diol, an organic diisocyanate and, if necessary, a chain extender are reacted at an excess molar ratio of isocyanate to obtain a urethane prepolymer having an isocyanate group at the terminal, and a part of the terminal isocyanate group is used as a chain terminator. After the reaction, this is added to polyethyleneimine, and the remaining terminal isocyanate groups are reacted with polyethyleneimine, which is a method for producing a urethane resin-modified polyethyleneimine. 8. The molecular weight of polyethyleneimine is 300 to
The method for producing a urethane resin-modified polyethyleneimine according to claim 7, which is 100,000. 9. The method for producing a urethane resin-modified polyethyleneimine according to claim 7, wherein the ratio of polyethyleneimine to urethane resin is in the range of 1/9 to 9/1 on a weight basis.