JPH02251515A - 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 prepolymer. CONSTITUTION:(A) A primary amino groups or primary and/or secondary amino groups-containing adduct which is prepared by the Michael reaction between a polyamine such as ethylenediamine and a (meth)acrylate monomer such as methyl (meth)acrylate 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 optional functional groups and/or side chains can be 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. Therefore, there are currently restrictions on the introduction of functional groups such as hydroxyl groups into polyurethaneurea resins for the purpose of introducing crosslinking components, improving pigment dispersibility, and adhesion properties. .

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

[Means to solve the problem]

In order to achieve the above object, the method for producing a polyurethane urea resin of the present invention uses a polyamine compound and a (meth)acrylic monomer obtained by the Miciae 1 reaction and remaining primary and/or secondary amino groups. is made to react with an addition product having at least two per molecule; and a urethane prepolymer obtained by reacting a high molecular weight diol with a diisocyanate compound.

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 pentaethylenehexazine, and mixtures of two or more thereof can be mentioned.

In addition, examples of the (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
Alkyl (meth)acrylates such as uralyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, persatic (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, tetrahydrofurfuryl ( Ether esters such as meth)acrylate, dialkyl pco*-Hfl such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di-2-ethylhexyl itaconate, β-hydroxyethyl (meth)acrylate, β-hydroxypropyl ( Hydroxy group-containing (meth)acrylates such as meth)acrylate, T-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as chloroethyl (meth)acrylate and (meth)acrylamide. , N5N-dimethylaminoethyl (meth)acrylate, N-methylol (meth)acrylamide,
Examples include (meth)acrylonitrile.

In the present invention, Mi
An addition product containing the desired functional group to be introduced is obtained by chae1 reaction, and this addition product is reacted with a polymeric diol as a chain extender to produce a polyurethaneurea resin containing the desired functional group to be introduced. In order to be used as a chain extender, the addition product must contain an active hydrogen-bearing amino group, i.e. a primary and/or a secondary amino group.
It is necessary that at least two remain per molecule.

Therefore, since (meth)acrylic monomers such as (meth)acrylic acid that have acidic groups that can react with amine compounds or form salts do not cause the Michael 1 reaction with polyamine compounds, the addition synthesis reaction in the present invention It is difficult to use in

Mic of polyamine compound and (meth)acrylic monomer
The hae1 reaction is carried out between room temperature and 150@C, and a diluting solvent can be used if necessary. Moreover, the molar ratio of the polyamine compound and the (meth)acrylic monomer is 1:0.
．． 01 to 1:2 is preferable, more preferably l:0.1
~l:1. If the amount of (meth)acrylic monomer is too small, the effect of the present invention will hardly appear, and (meth)
If the amount of the acrylic monomer is too large, the polyamine compound will have too little active hydrogen, 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 such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene propylene glycol, polyoxytetramethylene glycol, or ethylene of bisphael A. oxide, propylene oxide, alkylene oxide adducts such as ethylene propylene oxide, or dibasic acids such as adipic acid, phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, succinic acid, and glutaric acid, and ethylene glycol, diethylene glycol, and 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
- Condensates obtained by esterification reaction with diols such as trimethylbentanediol and hydrogenated bisphenol A, and polyester-type diols such as caprolactone, valerolactone, and methylvalerolactone polymers obtained using these diols as initiators, or polycarbonates. Examples include diol, polybutadiene diol, and the like.

The molecular weight of these diols is in the range of 300-5000°, preferably 500-3000. 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-Trimethylhexamethylene diisocyanate, lysine diisocyanate, etc., 1,4-cyclohexane diisocyanate, inphorone 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. In addition, there is no problem in using a suitable 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 (meth)acrylic monomer alone as a chain extender, known chain extenders can also be used in combination, such as ethylene glycol, diethylene glycol, propylene glycol, 1.3-propanediol, l,4-butanediol, l,3-butanediol, 1,6-hexanediol, 19-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.

(2) Introducing an N,N-dimethylaminoalkyl group makes it possible to improve pigment dispersibility and make it water-soluble through cationization.

(2) When an N-methylolamide group is introduced, it can be used as a thermosetting resin using a melamine resin, a polyisocyanate compound, etc. as a curing agent.

■Introducing a nitrile group improves pigment dispersibility.

- 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! Synthesis of urethane prepolymers by reaction of diisocyanate compounds and polymeric diols.

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 fourth flask of No. 21 equipped with a stirrer, thermometer, Dimroth, and N8 gas inlet tube, and the mixture was heated at 90° without passing N2 gas. C
The reaction was carried out for 5 hours to obtain a urethane prepolymer with a free @NCO content of 5.5% (this value is almost the same as the calculated value when all hydroxyl groups react with incyanate groups).

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 dissolved.

Synthesis Example 1-2 The same procedure as Synthesis Example 1-1 was used except that 573 parts of polyester diol obtained from 1,4-butanediol and adipic acid having an average molecular weight of 2000 and 127 parts of inphorone diisocyanate *-) were used. A reaction was carried out to obtain a urethane prepolymer with a free NGO content of 3.4%, and a solution of methyl ethyl ketone and ethyl acetate was prepared in the same manner as in Synthesis Example 1-1.

Synthesis Example 2 Synthesis of an addition product (U4 extender) by reaction of a polyamine compound and a (meth)acrylic monomer.

Synthesis Example 2-1 364 parts of inphorondiamine was charged into a four-bottom flask equipped with a stirrer, a thermometer, a Dimroth, and an N gas inlet tube, and the temperature was raised to 70°C to prepare N,N-dimethylaminoethyl methacrylate. 336 parts were dropped over 30 minutes,
The reaction was further carried out at 70''C for 5 hours.

As a result, a transparent liquid with a viscosity of B-C (25°C1 Gardner-Holdt method) was obtained.

Synthesis Example 2-2 194 parts of ethylenediamine and 506 parts of N,N-dimethylaminoethyl methacrylate were reacted in the same manner as in Synthesis Example 2-1 to obtain a transparent liquid with a viscosity of A-H.

Synthesis Example 2-3 465 parts of inphorondiamine and 235 parts of β-hydroxyethyl methacrylate were reacted in the same manner as in Synthesis Example 2-1 to obtain a transparent liquid with a viscosity of M.

Synthesis Example 2-4 194 parts of ethylenediamine and 506 parts of β-hydroxyethyl methacrylate were reacted in the same manner as in Synthesis Example 2-1 to obtain a transparent liquid with a viscosity of -L''.Synthesis Example 2-5 340 parts of isophorodiamine and 340 parts of 2-ethylhexyl acrylate was reacted in the same manner as in Synthesis Example 2-1 to obtain a transparent liquid with a viscosity of E.

Synthesis Example 2-6 183 parts of ethylenediamine and 517 parts of 2-ethylhexyl acrylate were reacted in the same manner as in Synthesis Example 2-1 to obtain a transparent liquid with a viscosity of CD.

Synthesis Example 2 - 515 parts of finphorondiamine, 1 part of diethylenetriamine
Synthesis Example 2: 6 parts of mixed liquid and 169 parts of acrylonitrile
A transparent liquid having a viscosity of B was obtained by reacting in the same manner as in -1.

Synthesis Example 2-8 261 parts of ethylenediamine and 439 parts of N-methylolacrylamide were charged into the same reaction apparatus as in Synthesis Example 2-1, heated to 100°C, and reacted for 5 hours.
A transparent liquid with a viscosity of D was obtained.

Synthesis Example 2-9 460 parts of metaxylene diamine and 240 parts of acrylamide
The reaction mixture was reacted in the same manner as in Synthesis Example 2-8 to obtain a transparent liquid having a viscosity of DH.

Example 1 Example of reaction between urethane prepolymer and addition product (114 extender).

420 parts of the prepolymer (Synthesis Example 1-1), 110 parts of methyl ethyl ketone, and 110 parts of ethyl acetate were charged into a 1 liter flask equipped with a stirrer, a thermometer, a Dimroth, and an N gas inlet tube, and when the temperature was raised to 50°C, the addition formation occurred. A mixed solution of 36 parts of Synthesis Example 2-1, 60 parts of toluene, 91 parts of methyl ethyl ketone, and 3 parts of n-butylamine was added. Thereafter, the reaction was carried out at 50° C. for 6 hours, and it was confirmed that the nonvolatile content was 30% and the viscosity was constant, and the completion of the reaction was confirmed. This viscosity is N-3 (Gardner-Hold method 25°C)
Met.

In this way, a tertiary amino group could be introduced into the polyurethaneurea resin.

Example 2 A urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 18 parts of the addition product (Synthesis Example 2-2), 60 parts of toluene, 47 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 5-T (Gardner-Hold method, 25°C).

In this way, a tertiary amino 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 35 parts of the addition product (Synthesis Example 2-3), 60 parts of toluene, 89 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 P (Gardner-Hold method, 25°C), and the hydroxyl value (solid content) was 20.

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

Example 4 Urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 16 parts of the addition product (Synthesis Example 2-4), 60 parts of toluene, 42 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 L”-M (Gardner-Hold method, 25”c
), and the hydroxyl value (solid content) was 22. In this way, primary hydroxyl groups could be introduced into the polyurethaneurea resin.

Example 5 A urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 25 parts of the addition product (Synthesis Example 2-5), 60 parts of toluene, 63 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 T-U (Gardner-Hold method, 25°C).

In this way, it was possible to introduce an alkyl group into the polyurethaneurea resin.

Example 6 Urethane prepolymer (Synthesis Example 1-1) was used, except that a mixed solution of 32 parts of the addition product (Synthesis Example 2-6), 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.

The viscosity was N (Gardner-Hold method, 25°C). In this way, alkyl groups could be introduced into the polyurethaneurea resin.

Example 7 Urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 16 parts of the addition product (Synthesis Example 2-7), 60 parts of toluene, 42 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 Q (Gardner-Hold method, 25°C). In this way, it was possible to introduce nitrile groups into the polyurethaneurea resin.

Example 8 A urethane prepolymer (Synthesis Example 1-1) was used, except that a mixed solution of 19 parts of the addition product (Synthesis Example 2-8), 60 parts of toluene, 51 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 of the second product was VW (Gardner-Holdt method, 25°C), and the hydroxyl value (solid content) was 29.

In this way, methylolamide groups could be introduced into the polyurethaneurea resin.

Example 9 Urethane prepolymer (Synthesis Example 1-2) was used, except that a mixed solution of 15 parts of the addition product (Synthesis Example 2-9), 60 parts of toluene, 40 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 S (Gardner-Hold method, 25°C). In this way, amide groups could be introduced into the polyurethaneurea resin.

(Effects 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 resins, and resins suitable for each use can be designed and manufactured. I can do it.

Claims (2)

[Claims] (1) 1 obtained by the Michael reaction of a polyamine compound and a (meth)acrylic monomer and remaining
At least 2 primary and/or secondary amino groups per molecule
1. A method for producing a polyurethane urea resin, which comprises reacting an addition product with a urethane prepolymer obtained by reacting a high molecular weight diol and a diisocyanate compound. (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.