JPS6195018A - Polyurethane resin solution - Google Patents

Abstract

PURPOSE:The titled solution useful as printing ink, etc., having improved adhesiveness, printability, and adaptability to laminate processing, obtained by reacting a specific polyurethane resin containing a free amino group with a halogenated epoxy compound. CONSTITUTION:(A) (i) A high-molecular-weight diol having 300-3,000 molecular weight is reacted with (ii) an organic isocyanate, and (iii) a chain extender to synthesize a free amino group-containing polyurethane resin of elastomer type, the amino group is further reacted with (B) a halogenated epoxy compound, to give the aimed solution containing a halogen element and a free hydroxyl group. A triamine is preferably used as the component (iii), so that the halogen element and the free hydroxyl group are preferably introduced to the side chain of the aimed polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane resin solution, and in particular, it is an object of the present invention to provide a polyurethane resin solution useful as a binder for various plastic films, sheets, or coatings for various synthetic resin products. In recent years, with the diversification of packaging containers and the increasing functionality of synthetic resin products such as synthetic leather, the printing inks and various coating agents used to decorate or protect the surfaces of plastic films, etc., are also required to have higher performance and quality. It is becoming more and more required.

Regarding printing ink, we use it to make packaging containers beautiful,
It has become necessary to respond to higher grade products, adhesion to various composite films, and suitability for various post-processing.

These various suitability are mainly determined by the binder resin used for printing inks and the like, and polyurethane resins have conventionally been used as binder resins for such uses. Conventional polyurethane resins are made by reacting polyol organic polyisocyanate with polyamine, which is a chain extender, if necessary, but printing inks using these polyurethane resin solutions as binders have a high resistance to nylon, polyester films, etc. Although it has sufficient adhesiveness, it does not have sufficient adhesiveness to polyethylene and polypropylene films, which are general-purpose films, and does not have sufficient suitability for 2-laminate processing.

In addition, the pigment dispersibility was insufficient, and there were problems in various printing suitability or coating suitability. Conventionally, methods of adding surfactants or other additives have been used to solve problems such as pigment dispersibility.
Such addition causes deterioration of the physical properties of the film, such as its suitability for boiling and retorting in food containers and the like. In addition, as a method of improving the polyurethane resin itself, the use of polyurethane having a hydroxyl group at the end has been attempted, but this has not yet been sufficient and has had problems.

The present invention was made to solve the above-mentioned problems with polyurethane resin solutions, and the present invention was completed by discovering that a polyurethane resin solution having a specific functional group solves the above-mentioned problems.

That is, the present invention synthesizes an elastomer-type polyurethane resin having free amino groups by reacting a high molecular weight diol with a molecular weight of 300 to 3000, an organic diisocyanate, and a chain extender, and further halogenated epoxy to the amino groups. The present invention aims to provide a polyurethane resin solution having a halogen element and a free hydroxyl group, which is obtained by reacting a compound.

The polyurethane resin according to the present invention includes high molecular weight diol,
Either react an organic diisocyanate to synthesize a prepolymer having -NCO groups at the end, and react it with a polyamine, which is a chain extender, or react each of these components simultaneously. 57. Two, two! To obtain the resin, polyethylene resin having free amino groups was obtained by adding polyamine, which is a chain extender, in excess of the stoichiometric amount, and then reacted with a halogenated ≠ xy compound. That's what you get.

As the components of the polyurethane resin according to the present invention, all conventionally known components can be used. Among the high molecular weight diol components, polyether diols include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyoxyethylene glycol, polyethylene glycol, etc. Polyoxyalkylene glycols such as oxypropylene glycol, polyoxyethylene propylene glycol, polyoxytetramethylene glycol, alkylene oxide adducts of bisphenol A such as ethylene oxide, propylene oxide, and ethylene propylene oxide, or polycaprolactone diol,
Examples of polyester diols include adipic acid, m-hydrophthalic acid, isophthalic acid, hamaric acid, hexamaric acid, and co-hydrophthalic acid. It refers to those obtained by condensation reaction with dibasic acids such as phosphoric acid and glycols such as ethylene glycol, diethylene glycol, propylene gelicol, 1.4 ph/hexane diol, neopentyl glycol, and 1.6 hexane diol. However, the molecular weight of these polyether diols and polyester type diols is 300 to 5000, preferably 1000 to 2000.
If the molecular weight is less than 300, the polyurethane resin synthesized from it will have excessive cohesive force between the resins, resulting in poor adhesion and lamination suitability, and a large amount of residual solvent will be left on printed matter. There is a drawback. On the other hand, if the molecular weight is 5000 or more, the cohesive force between the resins will be insufficient and blocking will easily occur.

In addition, as the organic diinocyanate component, tolylene diinocyanate, diphenylmethane diisocyanate,
xylidine diisocyanate, methylene diisocyanate, inpropylene diisocyanate, hexamethylene diisocyanate, 2.2.4- or 2,4.4-trimethylhexamethylene diisocyanate, lysine diisocyanate), 1.4-cyclohexane diisocyanate, isophorone Examples include diisocyanate, 4,4-dicyclohexylmethane diincyanate, and the like.

In addition, from the standpoint of obtaining a resin with excellent solubility,
Alicyclic diincyanates such as inphorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate are preferred.

In addition, polyamines as chain extenders include ethylenediamine, propylenediamine, hexamethylenediamine,
Examples include inphorone diamine, dicyclohexylmethane diamine, diethylene triamine, triethylene triamine, tetraethylene pentamine, sigloherne triamine, etc., but trivalent or higher valent polyamines have a halogen element and a free hydroxyl group as the object of the present invention in the side chain. It is preferable because it is possible to introduce a polyurethane resin having
Particularly preferred is triamine. 'Also, examples of the halogenated epoxy compound used in the present invention include epichlorohydrin, epibromohydrin, and the like.

When obtaining the polyurethane resin solution specified in the present invention using the above-mentioned components, the amount of halogen elements and hydroxyl groups contained in the polyurethane resin is extremely important to achieve the purpose. The content of hydroxyl groups is preferably 0.1 to 10 per 10,000 molecular weight of the resin, and the content of hydroxyl groups is preferably 0.017 to 1.7% by weight in the polyurethane resin.

If it is below this range, the desired pigment dispersibility, lamination suitability, etc. cannot be obtained; In other words, it will reduce the water resistance.

Solvents used during the reaction include aromatic solvents such as benzene, toluene, and xylene, which are commonly used as solvents for printing inks, ester solvents such as ethyl acetate, n-propyl acetate, and butyl acetate, and methyl alcohol. ,
Examples include alcohol solvents such as ethyl alcohol, isopropyl alcohol, and n-butyl alcohol, and ketone solvents such as acetone, methyl ethyl ketone, and methyl imbutyl ketone, alone or in combination, but from the viewpoint of the working environment, ester solvents, alcohol A single solvent or a mixture of these solvents is most suitable.

When using the polyurethane resin solution specified in the present invention synthesized from the above components as a binder for printing ink or coating agent, various pigments, antiblocking agents, plasticizers, etc. may be added to the polyurethane resin solution as necessary. In addition, other resins such as nitrified cotton, maleic acid resin, salt-vinyl acetate copolymer, and other compatible resins can be added, dispersed, and mixed to produce printing inks and coating agents. be. The printing ink or coating agent thus obtained solves the problems of conventional polyurethane resins and has pigment dispersibility, film performance, printability or coating suitability, and other suitability.

Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example-1 Adipic acid, a total of 200 parts of polyester diol with an average molecular weight of 2000 obtained from 1,4-butanediol, and 44 parts of inphorone diisocyanate were placed in a 17-four-bottle flask equipped with a stirrer, thermometer, Dimroth, and N2 gas inlet tube. After cooling, 248 parts of ethyl acetate was added to dissolve uniformly, 165 parts of Improvil alcohol and 25.8 parts of isophorone diamine were added, and further 7.4 parts of epichlorohydrin was added. The reaction was completed and the desired urethane resin was obtained.

The obtained resin had a solid content of 40% by weight and a temperature of 40 voids at 25°C.
The solution contained 2.9 chlorine atoms per 10,000 molecular weight and 0.49% by weight of hydroxyl groups.

(Polyurethane resin solution A) Example 2 A polyurethane resin solution B was prepared using the following charging composition in the same manner as in Example 1.

Polyoxytetramethylene glycol (molecular weight 2,000) 200.0 parts Isophorone diisocyanate 44.4 parts Isophorone diamine 23.8 parts Ethyl acetate
248.0 parts epichlorohydrin
The resin obtained in 7.4 parts was a solution having a solid content of 40% by weight, a molecular weight of 2.9 chlorine atoms per 10,000, and a hydroxyl group of 0.4% by weight at 50 voids/25°C.

Example 3 A polyurethane resin solution C having a functional group also in the side chain was prepared using the following charging composition in the same manner as in Example 1.

Polyester diol of Example 1 200.0 parts Isophorone diisocyanate 44.4 parts Isophorone diamine 17.0 parts Diethylenetriamine
4.0 parts ethyl acetate 2
44.0 parts Isopropyl alcohol 162.0
Part epichlorohydrin 5.6 parts The obtained resin has a solid content of 40% by weight and a mucilage of 30 poise/25°C.
The solution contained 4.4 chlorine atoms per min-f-@10,000 and 0.75% by weight of hydroxyl groups.

Comparative Example 1 Using the same equipment as in Example 1, 200.0 parts of the same polyester diol and 4 parts of isophorone diisocyanate were prepared.
4.4 parts of ethylene glycol was charged and reacted for several hours while introducing N2 gas, and further 9.1 parts of ethylene glycol was charged and the reaction was carried out to obtain a polyurethane having a hydroxyl group at the (+ terminal).
83 parts were added and uniformly dissolved to obtain the desired polyurethane resin.

The obtained resin had a hydroxyl group content of 0.57 and a solid content of 4 by weight.
The solution was 0% by weight and a viscosity of 10 poise/25°C.

(Polyurethane resin solution) Comparative Example 2 The following materials were prepared in the same manner as in Example 1, with a solid content of 40% by weight that does not have a functional group at the end, and a viscosity of 50 poise/2.
Polycritan resin solution E was prepared at 5°C.

Polyester diol of Example 1 200.0 parts Isophorone diisocyanate 44.4 parts Ethyl acetate
234.0 parts isopropyl alcohol
157.0 parts isophorone diamine
13.6 parts Moptilamine 2.9 parts Comparative Example 3 The following materials were prepared in the same manner as in Example 2, and a polyurethane resin solution having a terminal flukoxyl group with a solid content of 40% by weight and a viscosity of 35 voids/25°C was prepared. F was produced.

Polyoxytetramethylene glycol (molecular weight 2,00
0) 200.0 parts inphorone diisocyanate 44.4 parts inphorone diamine
13.6 parts ethyl acetate 23
2.0 parts Inoflovir alcohol 155.0 parts Evaluation test Each of the polyurethane resin solutions A-F obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was used as a binder for all printing inks, and the performance of each resin was evaluated. I did it. Printing inks are manufactured by mixing and kneading the following compositions.

Composition of white ink Polycretan tM fat solution 30 parts Isoflovir alcohol 25 parts Titanium oxide
30 parts Ethyl acetate 20 parts Blue ink composition Polyurethane resin solution 1 30 parts Isopropyl alcohol 25 parts Chanin blue
10 parts ethyl acetate 35 parts Using each printing ink, print on various films,
Adhesion, suitability for various prints, suitability for 2-lamination, and suitability for boiling and retorting were evaluated, and the results are shown in Table 1.

In addition, each evaluation method is based on the following method.

1) Adhesion After each test ink was printed on a specified film using a gravure proofing machine and left for one day, sellotape was applied to the printed surface and when this was rapidly peeled off, the printed film did not come off at all. Those that were not present (◎), those that remained on the film by more than ao% (0), those that remained on the film by 50 to 80 inches (Δ), 2
Those in which only 0% or less remained were indicated as (x).

2) Printing suitability ■ Color development... In order to evaluate pigment dispersibility,
Compare the transparency and density of prints.

■ Gradation reproducibility: Compare the gradation reproducibility by printing with a gravure plate that has continuous gradation.

■ Plate bleatability --- Compare the degree of transfer of blue ink to the white board.

The above-mentioned evaluation of each printing aptitude is evaluated as ◎ for the best one, 0 for each aptitude that does not interfere with printing, Δ for each aptitude that is insufficient, and × for no aptitude.

3) Extrusion lamination strength For each printed matter, use imine-based AC agents for OPP and inciamate-based AC agents for PET%NY, and laminate molten≠lyethylene using an extrusion laminating machine.After 3 days, cut the sample into 15w1 width, and Yasuda T-shaped peel strength was measured using a peel tester manufactured by Seiki Co., Ltd.

4) Dry lamination strength A CPP film was laminated on each printed matter using a dry lamination machine using a urethane adhesive, and the peel strength was measured in the same manner as the measurement of the 2-laminate strength after 3-day extrusion.

5) Boiling suitability and retort suitability After lamination, the printed matter is made into a bag, a water/oil mixture is put inside, and the bag is sealed.
After heating for 150 minutes at 120° C. for 30 minutes for retort suitability, the presence or absence of laminate floating was judged from the appearance. The evaluation was rated as ○ if there was no lamination lifting at all, and Δ if the lamination removal was observed in the form of pinholes.

February 27, 1985 1. Display of the case 1982 Patent Application No. 216948 2, Name of the invention Polyurethane Tree Ill Solution 3, Person making the amendment Relationship to the case Patent applicant 530 Address 2-6-2-4 Higashitenma, Kita-ku, Osaka , date of amendment order January 9, 1985 (January 1, 1985)
(Shipped on the 29th of the month) 5. Subject to correction

Claims (2)

[Claims] (1) A high molecular weight diol having a molecular weight of 300 to 3000, an organic diisocyanate, and a chain extender are reacted to synthesize an elastomeric polyurethane resin having free amino groups, and the amino groups are further reacted with a halogenated epoxy compound. A polyurethane resin solution containing a halogen element and free hydroxyl groups. (2) The polyurethane resin solution according to claim 1, which uses triamine as a chain extender and introduces a halogen element and a free hydroxyl group into the side chain.