JPH02251516A - Production of polyurethane urea resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin which is suitable for printing ink and a coating agent for plastic films, because of its improved pigment dispersion and adhesion by allowing a specific amino group-containing adduct to react with a urethane polymer. CONSTITUTION:(A) A two or more primary amino groups- or primary and/or secondary amino groups containing adduct which is prepared by addition reaction between a polyamine such as ethylenediamine and a monoepoxy compound such as ethylene oxide is allowed to react with (B) a urethane prepolymer from the reaction of a high molecular weight diol such as polyethylene glycol, preferably of 300 to 5,000 molecular weight, with a diisocyanate such as toluene diisocyanate to give the subject resin into which functional groups and/or side chains can be optionally introduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a polyurethaneurea resin to be applied to printing inks or coating agents used to coat various plastic films and the like.

[Conventional technology]

In recent years, as plastic materials have become more popular, the need for printing or coating them has increased. Polyurethane urea resins have excellent adhesion to plastics and film strength, and are therefore in increasing demand as printing inks for plastics and binders for coating materials.

Polyurethane urea resin is usually composed of polyether diol or polyester diol and diisocyanate, and the manufacturing method is to first perform a urethanization reaction by utilizing the difference in the reaction of amine and hydroxyl groups to isocyanate.
Next, a urea reaction is performed. These raw materials are appropriately combined to obtain polyurethane urea resins that meet each required performance.

Due to the manufacturing method of this polyurethane urea resin, the urethanization reaction is carried out with an excess of isocyanate, so no hydroxyl groups remain, and it is difficult to introduce functional groups such as hydroxyl groups. The concentration of the functional groups had to be extremely low.

Therefore, a technique for introducing hydroxyl groups into polyurethane urea resin has been proposed (Japanese Patent Publication No. 8346/1983).

[Problem to be solved by the invention]

Although this technique can certainly introduce only hydroxyl groups, it has not been possible to freely introduce various functional groups and side chains. Therefore, there are restrictions on the introduction of various functional groups such as hydroxyl groups and various side chains into polyurethaneurea resins for the purpose of introducing crosslinking components, improving pigment dispersibility, adhesion, and other properties. The current situation is that it exists.

The present invention is a method for producing a polyurethaneurea resin, which allows various functional groups and side chains to be freely introduced into the polyurethaneurea resin, and enables the design and production of a wide range of resins tailored to each application. The purpose is to provide

[Means for Solving the Problems] In order to achieve the above object, the method for producing a polyurethaneurea resin of the present invention provides a method for producing a polyurethaneurea resin obtained by reacting a polyamine compound and a monoepoxy compound and remaining primary and/or An addition product having at least two secondary amino groups per molecule; A urethane prepolymer obtained by reacting a high molecular weight diol with a diisocyanate compound;
It causes a reaction.

Although any conventionally known components can be used in the present invention, they will be specifically explained below.

As a polyamine compound, ethylenediamine 1.2-
Propylene diamine, 1,3-propanediamine, 1.
Straight chain aliphatic diamines such as 4-butanediamine and hexamethylene diamine, isophorone diamine, dicyclohexylmethane-4°4°-diamine, isopropylidene dicyclohexyl-4,4°-diamine, l,4-diaminocyclohexane , 1.3-bisaminomethylcyclohexane, alicyclic diamines such as aminoethylpiperazine,
Straight-chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine, and mixtures of two or more thereof are exemplified.

Examples of monoepoxy compounds include alkylene oxides such as ethylene oxide, propylene oxide and butane oxide, olefin oxides such as styrene oxide, alkyl glycidyl ethers, allyl glycidyl ethers, phenyl glycidyl ethers and their derivatives, alkoxy polyalkylene polyethers, etc. There are glycidyl ethers and glycidyl esters such as benzoic acid glycidyl ether and persatic acid glycidyl ester, and these may be used in combination.

In the present invention, an addition product containing the desired functional group to be introduced is obtained by reacting the above-mentioned polyamine compound with a monoepoxy compound containing the desired functional group, and this addition product is used as a chain extender to combine with a polymeric diol. A polyurethane urea resin containing a functional group to be introduced by reaction is produced. In order to be used as a chain extender, the addition product must have at least two remaining amino groups with active hydrogen, i.e., primary and/or secondary amino groups per molecule. .

The reaction between the polyamine compound and the monoepoxy compound is carried out between room temperature and 150°C, and a diluting solvent may be used if necessary. Further, the molar ratio of the polyamine compound to the monoepoxy compound is preferably 1:0.01 to 1:2, more preferably 1:0.1 to 1:1. If the amount of the monoepoxy compound is too small, the effect of the present invention will hardly be exhibited, and if the amount of the monoepoxy compound is too large, the active hydrogen of the polyamine compound will be too small, making it difficult to increase the molecular weight during chain extension.

Examples of high molecular weight diols include polyethylene glycol,
Polyalkylene glycols such as polypropylene glycol, polyether type diols such as polyoxyalkylene glycols, polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene propylene glycol, polyoxytetramethylene glycol, or bisphael A. Alkylene oxide adducts such as ethylene oxide, propylene oxide, and ethylene propylene oxide, or dibasic acids such as adipic acid, phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, succinic acid, and glutaric M, and ethylene glycol, diethylene glycol, Propylene glycol, 1,3-propanediol, 1,4-butanediol, 1゜3-butanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-bentane Diol, 3.3.5
-) Condensates obtained by esterification reactions with diols such as limethylbencune diol and hydrogenated bisphenol A, and polyester-type diols such as caprolactone, valerolactone, and methylvalerolactone polymers obtained using these diols as initiators. , borica-bonate diol, polybutadiene diol and the like.

The molecular weight of these diols ranges from 300 to 5,000, preferably from 500 to 3,000. If the molecular weight is less than 300, the printability and coating suitability of the resulting polyurethane urea resin will be poor, and if the molecular weight is more than 5,000, the resulting urethane resin will tend to cause blocking, which is not preferred.

As the diisocyanate compound, aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, methylene diisocyanate, isopropylene diisocyanate, hexamethylene diisocyanate, 2.2.4 or 2.
, 4.4-) Aliphatic diisocyanates such as lymethylhexamethylene diisocyanate and lysine diisocyanate, 1.4-cyclohexane diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, 4.4°-dicyclohexylmethane diisocyanate, etc., and two or more of these. Mixtures may be mentioned.

The reaction of the above-mentioned high molecular weight diol and diisocyanate compound to obtain a urethane prepolymer is usually carried out at room temperature to
It is carried out at a temperature of between 20°C and preferably between 60 and 100°C from the viewpoint of production time and control of side reactions. Also,
There is no problem in using an appropriate solvent or catalyst.

Further, the reaction between the addition product, which is a chain extender, and the urethane prepolymer is preferably carried out in a suitable solvent at room temperature to 80°C.

In addition to using the addition product of a polyamine compound and a monoepoxy compound alone as a chain extender, a known chain extender may also be used in combination. For example, ethylene glycol, diethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, 1,6-hexanediol,
1,9-nonanediol, neopentyl glycol, 3
-Methyl-1,5-bentanediol, 3,3.5-trimethylbentanediol, hydrogenated bisphenol A type diol, water, hydrazine, etc. can be used in combination.

Furthermore, according to the method of the present invention, which allows for the combined use of various pigments, other resins, additives, etc., various functional groups and/or side chains can be introduced, as exemplified below. It is possible to design and manufacture resins tailored to each application.

(2) If a hydroxyl group is introduced, it can be used as a thermosetting resin using melamine resin, polyisocyanate compound, etc. as a curing agent.

- By introducing an allyl group, it is possible to create a resin that is cured by ultraviolet rays or electron beams.

■If you introduce a side chain, phenyl group, or branched alkyl group,
Mechanical properties of resin can be freely designed.

〔Example〕

Examples will be shown below to specifically explain the present invention, but the present invention is not limited thereto. Note that parts and percentages in each example are based on weight.

Synthesis Example 1 Synthesis of urethane prepolymer by reaction of diisocyanate compound and polymeric diol.

Synthesis Example 1-1 485 parts of polypropylene glycol with an average molecular weight of 1000 and 215 parts of isophorone diisocyanate were charged into a 2i four-bottle flask equipped with a stirrer, a thermometer, a Dimroth, and an Nt gas inlet tube, and the mixture was heated at 90°C while flowing Nt gas. The reaction was carried out for 5 hours, and a urethane prepolymer having a free @NCO content of 5.5% (this value almost coincides with the calculated value when all hydroxyl groups react with isocyanate groups) was obtained.

This urethane prepolymer was cooled to 70°C, and 350 parts of methyl ethyl ketone and 350 parts of ethyl acetate were added thereto and uniformly melted.

Synthesis Example 1-2 The reaction was carried out in the same manner as Synthesis Example 1-1 except that 573 parts of polyester diol obtained from 1,4-butanediol having an average molecular weight of 2000 and adipic acid and 127 parts of isophorone diisocyanate were used. @NCO content rate 3
．． A 4% urethane prepolymer was obtained, and a methyl ethyl ketone and ethyl acetate solution was prepared in the same manner as in Synthesis Example 1-1.

Synthesis Example 2 Synthesis of an addition product (chain extender) by reaction of a polyamine compound and a monoepoxy compound.

Synthesis Example 2-1 L! equipped with a stirrer, temperature needle, Dimroth, and Nt gas inlet tube! Into the fourth flask, 299 parts of isophorone diamine was charged and the temperature was raised to 70°C, and 401 parts of Cardura E (manufactured by Shell Chemical Co., Ltd.: Versatic acid glycidyl ester) was added dropwise over an hour while being careful not to generate heat. °C
The reaction was carried out for 5 hours.

As a result, a transparent liquid with a viscosity Z of -24 (25°C, Gardner-Holdt method) was obtained.

Synthesis Example 2-2 146 parts of ethylenediamine and 554 parts of Cardura E were reacted in the same manner as in Synthesis Example 2-1, and the viscosity ZtZi (25°
A clear liquid of C1 Gardner-Holdt method was obtained.

Synthesis Example 2-3 397 parts of isophorone diamine and 303 parts of butyl glycidyl ether were reacted in the same manner as in Synthesis Example 2-1, and the viscosity
A transparent liquid of Y (25°C, Gardner-Hold method) was obtained.

Synthesis Example 2-4 221 parts of ethylene diamine and 479 parts of butyl glycidyl ether were reacted in the same manner as in Synthesis Example 2-1, and the viscosity Z(2
A clear liquid was obtained at 5°C (Gardner-Holdt method).

Synthesis Example 2-5 470 parts of isophorodiamine and 15 parts of diethylenetriamine
and glycidol (manufactured by NOF ■) in the same manner as in Synthesis Example 2-1 to obtain a transparent liquid having a viscosity of Z (25°C, Gardner-Holdt method).

Synthesis Example 2-6 241 parts of ethylene diamine and 459 parts of allyl glycidyl ether were reacted in the same manner as in Synthesis Example 2-1, and the viscosity was 2-2.
．． A clear liquid was obtained.

Example 1 Example of reaction between urethane prepolymer and addition product (IN extender).

Stirrer, thermometer, Dimroth, N! 420 parts of prepolymer (Synthesis Example 1-1), 110 parts of methyl ethyl ketone, and 110 parts of ethyl acetate were placed in a No. 11 flask equipped with a gas introduction tube, and when the temperature was raised to 50"C, the addition product (Synthesis Example 2-1) was added. 47 parts of toluene, 108 u of methyl ethyl ketone, and 3 parts of n-butylamine were added.Then, the mixture was reacted at 50'C for 6 hours until the nonvolatile content was 3
At 0%, it was confirmed that the viscosity was constant, and the completion of the reaction was confirmed. This viscosity is H-1 (Gardner-Hold method, 2
5''C), and the hydroxyl value (solid content) was 26.

In this way, a secondary hydroxyl group could be introduced into the polyurethaneurea resin.

Example 2 Urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 22 parts of the addition product (Synthesis Example 2-1), 60 parts of toluene, 50 parts of methyl ethyl ketone, and 2 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

The viscosity was N (Gardner-Hold method, 25°C), and the hydroxyl value (solid content) was 13.

In this way, a secondary hydroxyl group could be introduced into the polyurethaneurea resin.

Example 3 A urethane prepolymer (Synthesis Example 1-1) was used, except that a mixed solution of 22 parts of the addition product (Synthesis Example 2-2), 60 parts of toluene, 50 parts of methyl ethyl ketone, and 3 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

This viscosity is P''-Q (Gardner-Hold method, 25℃)
and the hydroxyl value (solid content) was 18. In this way, secondary hydroxyl groups could be introduced into the polyurethaneurea resin.

Example 4 Urethane prepolymer (Synthesis Example!-2) was used, except that a mixed solution of 14 parts of the addition product (Synthesis Example 2-2), 60 parts of toluene, 32 parts of methyl ethyl ketone, and 2 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

The viscosity was 0 (Gardner-Hold method, 25°C), and the hydroxyl value (solid content) was 12.

In this way, a secondary hydroxyl group could be introduced into the polyurethaneurea resin.

Example 5 Urethane prepolymer (Synthesis Example!-1) was used, except that a mixed solution of 35 parts of the addition product (Synthesis Example 2-3), 60 parts of toluene, 82 parts of methyl ethyl ketone, and 3 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

This viscosity was S (Gardner-Holdt method, 25°C), and the hydroxyl value (solid content) was 27.

In this way, a secondary hydroxyl group could be introduced into the polyurethaneurea resin.

Example 6 Urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 22 parts of the addition product (Synthesis Example 2-3), 60 parts of toluene, 50 parts of methyl ethyl ketone, and 2 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

This viscosity is M-N” (Gardner-Hold method, 25”C
), and the hydroxyl value (solid content) was 18. In this way, secondary hydroxyl groups could be introduced into the polyurethaneurea resin.

Example 7 Urethane prepolymer (Synthesis Example 1-1) was used, except that a mixed solution of 22 parts of the addition product (Synthesis Example 2-4), 60 parts of toluene, 50 parts of methyl ethyl ketone, and 3 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

The viscosity was L (Gardner-Hold method, 25°C), and the hydroxyl value (solid content) was 28.

In this way, a secondary hydroxyl group could be introduced into the polyurethaneurea resin.

Example 8 A urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 14 parts of the addition product (Synthesis Example 2-4), 60 parts of toluene, 32 parts of methyl ethyl ketone, and 2 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

This viscosity is V-W (Gardner-Hold method, 25°C)
The hydroxyl value (solid content) was 1B.

In this way, a secondary hydroxyl group could be introduced into the polyurethaneurea resin.

Example 9 Urethane prepolymer (Synthesis Example 1-1) was used, except that a mixed solution of 28 parts of addition product (Synthesis Example 2-5), 60 parts of toluene, 72 parts of methyl ethyl ketone, and 3 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

This viscosity is X-Y (Gardner-Hold method, 25°C)
The hydroxyl value (solid content) was 54.

In this way, secondary hydroxyl groups and primary hydroxyl groups could be introduced into the polyurethaneurea resin.

Example 10 A urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 13 parts of the addition product (Synthesis Example 2-6), 60 parts of toluene, 35 parts of methyl ethyl ketone, and 2 parts of n-butylamine was added. The reaction was carried out in the same manner as in Example 1, and completion of the reaction was confirmed.

The viscosity was QR (Gardner-Holdt method, 25°C), and the hydroxyl value (solid content) was 19.

In this way, it was possible to introduce a secondary hydroxyl group and an allyl group into the polyurethaneurea resin.

〔Effect of the invention〕

As described above, according to the method of the present invention, various functional groups and/or side chains can be introduced into polyurethane urea resins, and resins suitable for each use can be designed and manufactured.

The polyurethane urea resin into which desired functional groups and/or side chains have been introduced in this manner can be used, for example, in special gravure inks, various plastic primers, and various coating agents. Furthermore, by utilizing various functional groups, it can also be used as a thermosetting resin using a melamine resin, a polyisocyanate compound, or the like as a curing agent.

Claims (2)

[Claims] (1) An addition product obtained by the reaction of a polyamine compound and a monoepoxy compound and having at least two remaining primary and/or secondary amino groups per molecule; a high molecular weight diol, and a diisocyanate compound and,
A method for producing a polyurethane urea resin, which comprises reacting a urethane prepolymer with; (2) The method for producing a polyurethaneurea resin according to claim (1), wherein the polymeric diol has a molecular weight of 300 to 5,000.