JP2001040057A - Method for producing polyurethane polyurea and use of polyurethane polyurea obtained by the method - Google Patents

Abstract

(57) Abstract: An object of the present invention is to provide a polyurethane polyurea which can be made water-soluble and which can form an ink coating film and the like having high water resistance and high adhesion to a substrate by using an organic solvent. Obtaining it without the step of removing, and providing an aqueous ink using the polyurethane polyurea. SOLUTION: A diamine compound having an ethylene oxide chain, a diisocyanate compound (b1) and a polyol (A) containing a diol (a1) other than polyethylene glycol and a diol (a2) having an ionizable dissociating group are used without solvent. With a diisocyanate compound (b
1) A method for producing a polyurethane polyurea, which comprises reacting with an urea compound (B) having an isocyanate group, which is reacted under excess conditions, at 130 to 220 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane polyurea which can be made water-soluble, and an aqueous printing ink using the polyurethane polyurea obtained by the method. The polyurethane polyurea obtained by the production method of the present invention can be formed into a coating film having excellent water resistance, organic solvent resistance and adhesion, while being water-soluble, that is, one that can be dissolved or dispersed in water. , Water-based inks, water-based adhesives, etc., and especially suitable for water-based printing inks.

[0002]

2. Description of the Related Art Polyurethane polyurea (hereinafter sometimes referred to as urethane urea resin) has an adhesive property to a substrate,
Because it has excellent wear resistance, impact resistance, and solvent resistance,
As paints, inks, adhesives, and various coating agents,
Widely used for paper, plastics, films, metals, textiles, etc. Conventionally, aqueous solutions, emulsions, colloidal desversions and the like of polyurethane polyurea obtained by dissolving or dispersing polyurethane polyurea in an aqueous medium (collectively referred to as aqueous solutions of polyurethane polyurea, etc.) are mainly composed of acetone, methyl ethyl ketone, n-methylpyrrolidone. , After producing polyurethane polyurea in an aromatic organic solvent, etc., it was obtained through a desolvation process and an aqueous process (Prog
ress in Organlc Coatings, 9 , 281, (198
1)).

[0003] By the way, polyurethane polyurea is aqueous
To achieve this, the part having a high affinity for the aqueous medium is
Must be introduced into urethane polyurea, and generally large
There are two approaches. One is polyurethane polyurethane
A-(CH_TwoCH_TwoO)_n-The method of introducing
One of the raw materials for urethane polyurea is-(CH_TwoCH_TwoO)
_nUsing a diol component or a diamine component having
As a result, in the polyurethane polyurea,-(CH_TwoCH_Two
O)_n-Can be introduced. The other is an aqueous medium
Polyurethane polyurea dissociable in the body
The method of introducing such polyurethane polyurethane
For rare, use a raw material having an ionizable dissociation group.
And can be obtained by: Often ionizable
Raw materials having a functional dissociation group include carboxyl groups,
Sulfonic acid group (-SO _ThreeH) or having a tertiary amino group, etc.
Diols are used. Polyurethane polyurea obtained
Neutralize these ionizable dissociative groups after
Dissolving polyurethane polyurea in aqueous media
It can be solved or dispersed.

[0004] However, polyurethane polyurea is not enough.
-(CH_TwoCH_TwoO) _n-Or ionization
When one of the possible dissociating groups is introduced, the resulting coating
The water resistance of the film becomes insufficient. On the other hand, the reason is detailed.
Although not elucidated in detail,-(CH_TwoCH_TwoO)_n-And a
Polyurethanes that can be made water-soluble by ionizable dissociating groups.
Polyurea is-(CH_TwoCH_TwoO)_n-Or ionizable
Polyurethane poly into which either one of the dissociating groups is introduced
Can form a coating film with higher water resistance than urea
You. Therefore,-(CH_TwoCH_TwoO)_n-And ionization
Aqueous polyurethane polyurea with possible dissociative groups
Has been applied to printing inks etc.
Was.

An aqueous solution of polyurethane polyurea, that is, an aqueous solution of polyurethane polyurea,
In terms of use and handling, it is superior to the conventional organic solvent solution of polyurethane polyurea.However, since a large amount of organic solvent is used in the production process, after obtaining polyurethane polyurea, As described above, a step of removing the organic solvent was required. This desolvation step requires labor, time and cost, and thus has problems in terms of workability, productivity and economy. In addition, there is also a big problem in how to treat the organic solvent removed during aqueous conversion, whether reused or incinerated. Therefore, there has been a strong demand for the development of a polyurethane polyurea suitable for paints, inks, adhesives, etc., which can be made water-soluble without going through a step of removing an organic solvent.

Here, for the purpose of omitting the step of removing the solvent, a method of simply not using an organic solvent such as acetone, methyl ethyl ketone, n-methylpyrrolidone, or an aromatic organic solvent may be considered. However,-(CH ₂ CH ₂ O) _n
A diol component having a-and a diol component having a carboxyl group or the like are generally incompatible with each other, so that when these are used in combination and a polyurethane polyurea is obtained simply without using an organic solvent, a uniform polyurethane polyurea is used. I couldn't get it. As a result, the aqueous solution or not only lacks storage stability as an aqueous dispersion,
When used as an ink, paint or the like, the adhesion to the substrate becomes insufficient.

[0007]

SUMMARY OF THE INVENTION The present invention is directed to a polyurethane polyurea which can be made water-soluble, and which removes an organic solvent from a polyurethane polyurea capable of forming an ink coating or the like having excellent water resistance and adhesion to a substrate. An object of the present invention is to provide an aqueous ink using the polyurethane polyurea without any additional steps.

[0008]

Means for Solving the Problems In view of the above objects, the present inventors have conducted intensive studies and as a result, have found that a polyol component having a diol component having an ionizable dissociable group such as a carboxyl group as an essential component, an isocyanate group and − (CH ₂ CH
₂ O) _n - and polyurea component having, by reacting at relatively high temperatures, found a method capable of producing a water-polyurethanes polyurea without passing through the step of removing the organic solvent, and completed the present invention . That is, the first invention provides an ethylene represented by the following general formula (1) in the absence of a solvent containing a diol (a1) other than polyethylene glycol and a polyol (A) containing a diol (a2) having an ionizable dissociating group. A urea compound having an isocyanate group (B) obtained by reacting a diamine compound having an oxide chain with a diisocyanate compound (b1) under an excess condition of the diisocyanate compound (b1);
A method for producing a polyurethane polyurea, which comprises reacting at 220 ° C.

Formula (1) H ₂ N—R— (OCH ₂ CH ₂ ) _n —O—R′—NH ₂ (wherein R and R ′ are each independently an alkylene group having 1 to 7 carbon atoms) And n is an integer of 1 to 500.)

According to a second aspect of the present invention, the diol (a1) other than polyethylene glycol contains 1,4-cyclohexanedimethanol and / or polytetramethylene glycol. Is the way.

A third aspect of the present invention is a polyurethane polyurea obtained by the production method according to the first or second aspect.

A fourth aspect of the present invention is an aqueous solution or dispersion of the polyurethane polyurea, wherein the polyurethane polyurea according to the third aspect is dissolved or dispersed in an aqueous medium.

A fifth aspect of the invention is the aqueous solution or dispersion of a polyurethane polyurea according to the fourth aspect, wherein the aqueous medium is an organic solvent having a hydroxyl group and water.

According to a sixth aspect, the organic solvent having a hydroxyl group is isopropyl alcohol, n-butyl alcohol,
An aqueous solution or dispersion of the polyurethane polyurea according to the fifth aspect, which is selected from the group consisting of ter-butyl alcohol.

A seventh aspect of the present invention is an aqueous printing ink comprising an aqueous solution or dispersion of the polyurethane polyurea according to any one of the fourth to sixth aspects.

[0016]

DETAILED DESCRIPTION OF THE INVENTION In a polyurethane polyurea,
_{(CH 2 CH 2 O) n} - as a way of introducing the, - (CH ₂ CH ₂
O) _n - and a method of using a diol component having a, - (CH ₂
Although there is a method using a diamine component having CH ₂ O) _n −, the former generally has poor compatibility with the diol component having a carboxyl group as described above. On the other hand,-(CH
₂ CH ₂ O) _n - As a method for obtaining a polyurethane-polyurea with a diamine component having further a diol component and a polyisocyanate component having a carboxyl group by reacting under the conditions of isocyanate groups over the isocyanate groups After obtaining a polyurethane having, the isocyanate group of the polyurethane and-(CH ₂ C
The method reacting a diamine with a component, and a diisocyanate compound _{- - H 2 O) n (} CH 2 CH 2 O) n - and diamine component having by reacting under the conditions of isocyanate groups over the, having isocyanate groups After polyurea is obtained, a diol component having a carboxyl group or the like may be reacted with an isocyanate group of the polyurea. However, in the case of the method, the viscosity of the reaction system sharply rises due to the formation of urea bonds in the latter half of the reaction, the reaction becomes difficult to control, the reaction tends to be non-uniform, and as a result, lumps are likely to occur In addition, there is a problem that a diamine component which lowers water resistance tends to remain. On the other hand, in the case of the urea bond, the rapid increase in viscosity of the reaction system can be avoided because the urea bond is already present, the reaction system is also likely to be uniform, and the diamine component that reduces the water resistance hardly remains. There are advantages.

The diol (a1) other than polyethylene glycol used in the present invention includes, for example, trimethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexane. In addition to diol, 1,4-cyclohexanedimethanol, polypropylene glycol, polytetramethylene glycol, etc., polycaprolactone, poly β-methyl-δ-
Lactone ring-opening polymer polyols such as valerolactone,
Polycarbonate diol and the like can be mentioned, and when 1,4-cyclohexanedimethanol of a cycloaliphatic is used, a polyurethane having high crystallinity and a large cohesive force can be obtained. Further, polyester diols obtained by condensing these diols with dibasic acids such as adipic acid, azelaic acid, sebacic acid, isophthalic acid, and terephthalic acid are exemplified.

As the diol (a2) having an ionizable dissociable group used in the present invention, for example, a diol having a carboxyl group, a sulfo group (—SO ₃ H), a tertiary amino group or the like is used. As the carboxyl group-containing diol, dimethylol alkanoic acid such as dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, and dihydroxypropionic acid; Dihydroxysuccinic acid and dihydroxybenzoic acid. Particularly, dimethylolpropionic acid, dimethylolbutanoic acid, and 2,2-dimethylolbutyric acid are preferable from the viewpoint of reactivity and solubility. Such tertiary amino group-containing diols include such alkyl (dihydroxyalkyl) amines. After obtaining the polyurethane polyurea, the polyurethane polyurea can be made aqueous by neutralizing the ionizable dissociative group derived from the diol (a2).
The diol (a2) having an ionizable dissociative group is 1 to 3 in a total of 100% by weight of the polyol (A) and a polyurea compound (B) having an isocyanate group described below.
It is preferable to use it so as to contain 0% by weight. If the amount is less than 1% by weight, the water-soluble ability of the polyurethane polyurea obtained by polyaddition tends to be insufficient, and a dispersion having a large particle size of the dispersed particles tends to be formed. As a result, the dispersion stability of the aqueous dispersion is easily impaired. On the other hand, when a coating film (film) is formed using an ink, a coating material or the like containing a polyurethane polyurea obtained using a diol (a2) exceeding 30% by weight, the water resistance of the coating film tends to be poor.

In the present invention, one of the polyols (A)
For example, in addition to the diol (a1) other than the above-described polyethylene glycol and the diol (a2) having an ionizable dissociative group, a polyol (a3) having three or more hydroxyl groups can be further used. When a polyol (a3) having three or more hydroxyl groups is used, the cohesive force of the obtained polyurethane polyurea increases, and when such a polyurethane polyurea is used for an aqueous printing ink or the like, rubbing resistance and scratch resistance of the coating film are improved. When a polyol (a3) having three or more hydroxyl groups is used, 0.05 to 100% by weight of the total of the polyol (A) and the polyurea compound having an isocyanate group (B) described below are used.
It is preferable to use 3% by weight. 0.
When the amount is less than 05% by weight, the collecting power is not so much improved as compared with the case where it is not used. When the amount exceeds 3% by weight, gelation tends to occur during the reaction with the polyurea compound (B) having an isocyanate group. Examples of the polyol (a3) having three or more hydroxyl groups used in the present invention include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, sorbitol and the like.

Next, the urea compound (B) having an isocyanate group used in the present invention will be described. Polyurethane polyurea using the urea compound (B) having an isocyanate group and the above-mentioned polyol (A) is excellent in elongation and strength as compared with a case where it does not have a urea bond. Particularly thin and tough coating films can be obtained from printing inks and paints. Urea compound having isocyanate group (B)
Can be obtained by reacting a diisocyanate compound (b1) with a diamine compound having an ethylene oxide chain represented by the general formula (1) under conditions of an excess of isocyanate groups. Specifically, it is preferable to add a diamine compound having an ethylene oxide chain represented by the following general formula (1) to an excess of the diisocyanate compound (b1) at room temperature. The molar ratio between the diamine compound and the diisocyanate compound (b1) is 1/3.
It is preferably about 1/50. When the ratio is less than 1/3, the viscosity of the obtained urea compound (B) having an isocyanate group becomes extremely high, or an aggregate is easily formed. Also,
If it exceeds 1/50, urea bonds and buret bonds derived from the amine compound are reduced, and the collecting power is reduced.

Examples of the diisocyanate compound (bl) used for obtaining the urea compound (B) having an isocyanate group include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, -Phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3 '
-Dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-biphenylenediisocyanate, 1,5-naphthalenediisocyanate,
Aromatic diisocyanate compounds such as 1,5-tetrahydronaphthalenediisocyanate, aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate (hereinafter referred to as IPDI), 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate (hereinafter, referred to as
Alicyclic diisocyanate compounds such as NBDI).

In the present invention, in addition to the above diisocyanate compound (bl), a trifunctional isocyanate compound (b2) can be used in combination, if necessary. Examples of the trifunctional isocyanate compound (b2) include: 1) an adduct type of trimethylolpropane, for example, Takenate D-160N (manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur HT (manufactured by Sumitomo Bayer Urethane Co., Ltd.), 2 ) Buret type, for example Takenate D-165N
(Manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur N3200
(Sumitomo Bayer Urethane Co., Ltd.) 3) Isocyanurate ring type, for example, VESTANA
TT1890 (manufactured by Huls Co., Ltd.) and the like. When the trifunctional isocyanate compound (b2) is used,
It is preferable to use the polyol (A) and the polyurea compound (B) having an isocyanate group in such a manner that 0.5 to 5% by weight is contained in 100% by weight in total. If it is less than 0.5% by weight, the cohesive strength of the obtained polyurethane polyurea is not so much improved as compared with the case where it is not used. On the other hand, if it exceeds 5% by weight, the viscosity tends to increase and the gelation tends to occur during the reaction with the polyol (A).

The diamine compound represented by the general formula (1) used for obtaining the urea compound (B) having an isocyanate group (hereinafter referred to as EO diamine compound) is
For example, it can be obtained by substituting the terminal hydroxyl group of polyethylene glycol with an amino group. General formula (1) H ₂ N—R— (OCH ₂ CH ₂ ) _n —O—R′—NH ₂ (wherein R and R ′ are each independently an alkylene group having 1 to 7 carbon atoms; n is an integer of 1 to 500.) The number of repeating ethylene oxide of the EO diamine compound, that is, n in the above general formula is 1 to 500, and preferably 20 to 100. It is preferable that n is large from the viewpoint of aqueous conversion, but it is preferable that n is not too large from the viewpoint of water resistance of the formed coating film. Examples of the alkylene group represented by -R- and -R'- bonded to both ends of the ethylene oxide chain include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, and 2-ethyl. Examples include a chain alkylene group such as tetramethylene, and a cycloalkylene group such as cyclotetramethylene, cyclopentylene, cyclohexylene, and methylcyclohexylene, and ethylene is preferable. For example, PEG1000 diamine, PEG2000 diamine and the like manufactured by NOF CORPORATION can be mentioned.

In the present invention, in addition to the above-mentioned EO diamine compound, if necessary, aliphatic diamines such as ethylenediamine, propylenediamine and hexamethylenediamine, alicyclic diamines such as isophoronediamine, aromatic compounds such as piperazine and diphenyldiamine may be used. Aromatic diamines can also be used in combination.

The reaction between the polyol (A) and the urea compound (B) having an isocyanate group is carried out at 130 to 220 ° C.
The reaction is preferably performed at 130 to 180 ° C. for 10 minutes to 2 hours. When both are reacted at a temperature lower than 130 ° C., the reaction system tends to have a high viscosity, and as a result, it is difficult to uniformly react. On the other hand, when the reaction is carried out at an excessively high temperature, not only does the urea compound (B) having an isocyanate group tend to be decomposed, but it is not preferable from the viewpoint of energy saving. Specifically, for example, it is preferable to add or drop the urea compound (B) having an isocyanate group in the polyol (A). In this case, when the urea compound (B) having an isocyanate group is added or dropped in the polyol (A), if the urea compound (B) having the isocyanate group is heated in advance, the viscosity of the compound (B) decreases. , Dripping and addition become easy. The polyurethane polyurea thus obtained may be a resin in which an allophanate bond, a buret bond, and the like are mixed in addition to a urethane bond and a urea bond.

The reaction between the polyol (A) and the polyurea compound having an isocyanate group (B) is sufficient without using a catalyst, but can be used if necessary. As the catalyst, a known metal catalyst or amine catalyst can be used. Among the metal catalysts, examples of organometallic catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), lead 2-ethylhexoate, 2-ethylhexyl titanate, and 2-ethylhexyl. Hexoate iron, 21-ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, etc., and inorganic metal catalysts such as stannous chloride, stannic chloride, and iron chloride Is mentioned. The end point of the reaction can be confirmed by disappearance of the NCO peak by viscosity measurement and IR (infrared) measurement.

The polyurethane polyurea obtained by reacting the polyol (A) with the urea compound having an isocyanate group (B) has a number average molecular weight of 5,000 to 2
000, and a number average molecular weight of 5,0
More preferably, it is from 00 to 18,000. When an aqueous printing ink containing a polyurethane polyurea having a number average molecular weight of less than 5,000 is used, the resulting coating film tends to have poor blocking resistance, retort resistance and the like. When the polyol (A) and the urea compound having an isocyanate group (B) are reacted in the absence of a solvent, the viscosity of the reaction system is generally higher than when the two are reacted in the presence of a solvent. When the viscosity is extremely high, it is difficult to sufficiently stir the mixture, and it is difficult to uniformly react. As a result, it takes more time to complete the reaction. Therefore, when the polyol (A) and the urea compound (B) having an isocyanate group are reacted in the presence of a solvent, the molecular weight of the obtained polyurethane polyurea is reduced when the two are reacted in the absence of a solvent. It is preferable to make it relatively small. That is, the number average molecular weight is 20,000.
It is preferable to keep it below. Further, when an aqueous printing ink containing a polyurethane polyurea having a number average molecular weight of more than 18,000 is used, resolubility or redispersion becomes difficult, so that the number average molecular weight is 18,000.
The following is preferred. The resolubility and the like means that when the printing ink attached to the printing plate roll or the like is dried during and after printing, the dried product is dissolved or dispersed again in the ink. When such resolubility or redispersibility deteriorates, printing is stopped, the plate rolls and the like must be frequently washed, and not only the workability tends to deteriorate, but also in the coating film after printing. Simulated objects are easily generated.

The polyurethane polyurea obtained as described above is prepared by adding-(CH ₂ CH _{2) in} 100% by weight of the polyurethane polyurea so as to be easily dissolved or dispersed in an aqueous medium as described later. O)-0.5
-15% by weight, preferably 2-10% by weight
More preferably, it is contained. Further, when the ionizable dissociating group is a carboxyl group, the acid value of the polyurethane polyurea is preferably 15 to 45 (mgKOH / g), more preferably 25 to 40 (mgKOH / g). .

The polyurethane polyurea obtained as described above may be dissolved or dispersed in an aqueous medium as it is, for example, after the urethanization reaction, or may be taken out as it is after the urethanization reaction. After taking it out, if it is a solid polyurethane polyurea at room temperature, it is cooled and pulverized, and the beret-like, granular, and
It may be in powder form. Thereafter, the solid or viscous polyurethane polyurea can be dissolved or dispersed in an aqueous medium to obtain an aqueous solution or dispersion of the polyurethane polyurea. Or kneading a solid or viscous polyurethane polyurea and a pigment that has undergone a drying step in the presence or absence of an aqueous medium, or kneading a solid or viscous polyurethane polyurea and an aqueous paste of a pigment In addition, a processed pigment (processed pigment) can be obtained.

The aqueous solution or dispersion of the polyurethane polyurea can be obtained by various methods as described below. (1) After the urethanization reaction, the polyurethane polyurea is taken out and the polyurethane polyurea is dissolved or dispersed in an aqueous medium. The aqueous medium refers to water or an organic solvent having water and a hydroxyl group. It is preferable to use only water from the viewpoint of simply “watering”, but it is preferable to use an organic solvent having a hydroxyl group in combination from the viewpoint of ensuring the solubility and dispersion stability of the polyurethane polyurea. In this case, after adding an organic solvent having a hydroxyl group to the polyurethane polyurea, water may be subsequently added, or a mixture of water and an organic solvent having a hydroxyl group may be added to the polyurethane polyurea, or water may be added to the polyurethane polyurea. After addition, an organic solvent having a hydroxyl group may be added, or a polyurethane polyurea may be added to the organic solvent having a hydroxyl group, and then water may be added, or a mixture of water and an organic solvent having a hydroxyl group. You may add polyurethane polyurea to
After adding water to the polyurethane polyurea, then an organic solvent having a hydroxyl group may be added, but after adding an organic solvent having a hydroxyl group to the polyurethane polyurea and dissolving the polyurethane polyurea in the organic solvent having a hydroxyl group,
Preferably, water is added to the polyurethane polyurea solution to dissolve or disperse the polyurethane polyurea in an aqueous medium. (2) In the case of the above (1), a basic compound for neutralizing the ionizable dissociable group or an acidic compound can also be used. In this case, the order of use and the order of addition of water, an organic solvent having a hydroxyl group, and a basic compound can be appropriately selected. (3) After the urethanization reaction, the polyurethane polyurea is dissolved or dispersed in an aqueous medium as a series of operations and steps without taking out the polyurethane polyurea. It is preferable to use an organic solvent having a hydroxyl group in combination. The order of addition can be selected as appropriate, but after adding an organic solvent having a hydroxyl group to the polyurethane polyurea and dissolving the polyurethane polyurea in the organic solvent having a hydroxyl group, water is added to the polyurethane polyurea solution to make the polyurethane polyurea aqueous, that is, aqueous. The point that it is preferable to dissolve or disperse in a medium is the same as in the case of the above (1). (4) In the case of the above (3), as in the case of the above (2), a basic compound or the like for neutralizing the ionizable dissociative group can be used. Again, water,
Use order of an organic solvent having a hydroxyl group, a basic compound,
The order of addition can be appropriately selected.

From the viewpoint of workability, the above (3) and (4) are preferable, and (4) is particularly preferable. Further, since polyurethane polyurea in a highly viscous state is often hardly compatible with water or a basic compound, etc., (a) an organic solvent having a hydroxyl group is first added to polyurethane polyurea in a highly viscous state. , Water and a basic compound, etc. at the same time, or (b) an organic solvent having a hydroxyl group is first added to the polyurethane polyurea, then water is added, and then a basic compound or the like is added. After first adding an organic solvent having a hydroxyl group to polyurea,
It is preferable to add a basic compound or the like and then add water, or (d) first add an organic solvent having a hydroxyl group to the polyurethane polyurea, and then add a mixture of water and a basic compound.

Examples of the organic solvent having a hydroxyl group used in the aqueous conversion include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene glycol and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether,
Ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether , Diethylene glycol mono-n-hexyl ether, 2,2,4-trimethylpentanediol
1,3-monoisobutyrate (Texanol, manufactured by Eastman Chemical Company) or the like can be used alone or in combination. Among these organic solvents having a hydroxyl group, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, and the like have a function of suppressing the viscosity of an aqueous solution of polyurethane polyurea or the like, or a function as a film forming aid or a coating aid. Butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether,
And 2,2,4-trimethylpentanediol-1,3
Monoisobutyrate is preferred, when using an aqueous solution of polyurethane polyurea in an aqueous printing ink,
Especially isopropyl alcohol, n-butyl alcohol,
It is preferred to use t-butyl alcohol. In addition to the organic solvent having a hydroxyl group, an organic solvent having no hydroxyl group can be used in combination, if necessary.

When a carboxyl group-containing diol is used as the diol (a2) having an ionizable dissociating group, the carboxyl group derived from the diol (a2) can be made aqueous by neutralizing with a basic compound. . Examples of the basic compound used include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine,
Octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2
-Methyl-1-propanol, morpholine and the like, and these can be used alone or as a mixture of two or more. It is preferable to appropriately select and use these basic compounds in consideration of the ease of compatibility with the polyurethane polyurea and the stability after dispersion in water. In neutralizing a diol having a carboxyl group such as dimethylolalkanoic acid, it is preferable to use 0.6 to 1.2 equivalents of a basic compound with respect to 1 equivalent of the carboxyl group.

When a tertiary amino group-containing diol is used as the diol (a2) having an ionizable dissociative group, the tertiary amino group derived from the diol (a2) is quaternized with an acidic compound or an alkylating agent. By conversion, it can be made aqueous.

In the present invention, it is preferable not to use a surfactant, but it is also possible to use a small amount of a surfactant in combination for the purpose of improving the stability of the aqueous dispersion of polyurethane polyurea. When a surfactant is used, there are a method of dissolving and adding the compound in an organic solvent having a hydroxyl group, a method of dissolving and dispersing in water and lacquering. Examples of the surfactant include anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonates, naphthalene sulfonates, and alkyl sulfosuccinates; polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, There are nonionic surfactants such as polyoxyethylene alkylphenyl ether and polyoxyethylene alkylphenyl ester.

The thus obtained polyurethane polyurea of the present invention is particularly useful as an aqueous printing ink, and has excellent adhesion to aqueous paints, vehicles for adhesives, binder resins, and polyolefins. Therefore, it can be applied to various primers.

[0037]

The present invention will be described in detail with reference to the following examples. “Parts” in the pottery and examples represent “parts by weight”. Example 1 In a 100 ml flask equipped with a stirrer and a nitrogen introducing tube,
Charge 32 parts of isophorone diisocyanate and at room temperature,
While stirring vigorously, 20 parts of PEG diamine 1000 (diamine compound having an ethylene oxide chain and having a number average molecular weight of 1000) was added to obtain a urea compound having an isocyanate group. Next, a four-necked 1000 ml flask equipped with a reflux condenser, a nitrogen inlet, a stirrer, and a thermometer was replaced with dry nitrogen, and the number average molecular weight was 2,000 as (a1).
(Hydroxyl value 56) polytetramethylene glycol 37
Parts and 11 parts of dimethylolbutanoic acid as (a2), and the temperature was raised to 160 ° C. Then, under stirring, the entire amount of the urea compound obtained above was added over 10 minutes, and after the addition, 190
C. and gradually reacted for another 20 minutes. The polyurethane polyurea having a number average molecular weight of about 13,000 (C
1) was obtained. Next, 300 parts of distilled water containing 6 parts of ammonia water were added while cooling to obtain an aqueous dispersion of polyurethane polyurea (C1) having a solid content of about 24% by weight.

The dispersibility and storage stability of the obtained aqueous dispersion were evaluated by the following evaluation methods and criteria, and the results are shown in Table 1. 1) Dispersibility: The presence or absence of lumps, the presence or absence of stain on the inner wall of the flask, and the like were visually evaluated. ◎: There is no occurrence of dust and stain on the inner wall of the flask, and the water dispersibility is very good. ：: No bumps occurred. Some deposits are formed on the inner wall of the flask, but the deposits can be quickly removed by washing with water and have good water suitability. Δ: Some lumps were generated, or a little deposit was formed on the inner wall of the flask, and the water dispersibility was slightly poor. X: Bubbles are generated or deposits are formed on the inner wall of the flask, and if washed with water, the deposits cannot be easily removed, and the water dispersibility is poor. 2) Storage stability The aqueous dispersion of the polyurethane was placed in a thermostat at 40 ° C for 30 days, and the degree of the precipitate was examined. ◎ There is no sediment. ○ Almost no sediment. △ A little precipitate is formed. X: A considerable amount of precipitate is formed.

Example 2 50 parts of an aqueous dispersion of the polyurethane (C1) obtained in Example 1, 20 parts of a phthalocyanine blue pigment (Rionol Blue KLH manufactured by Toyo Ink Mfg. Co., Ltd.), 0.1 part of an antifoaming agent And 29.1 parts of water were stirred with a homomixer at 7,000 rpm for 20 minutes to obtain a pigment dispersion. A mixed solvent of water / isopropyl alcohol = 1/1 was added to the pigment dispersion, and the mixture was adjusted to 19 seconds with Zahn Cup # 4 to obtain an aqueous ink. The obtained water-based ink was applied onto a treated OPP film (“Pyren P2161” manufactured by Toyobo Co., Ltd.) and a treated PET film (“Ester E5100” manufactured by Toyobo Co., Ltd.) in a # 7 barco overnight. After drying in a drying oven at 10 ° C. for 10 minutes, the adhesion of the ink layer to each film, the resistance to rubbing, and the color development were evaluated. Table 1 shows the results.

3) Evaluation of Adhesion of Ink Layer to OPP and PET Films After a cellophane tape was attached to the ink layer, this was peeled off, and the peeling state of the ink layer was visually evaluated. ◎ Does not peel at all. ○ Almost no peeling. △ Peel a little. X: It peels considerably.

4) Evaluation of resistance to rubbing The ink layer on the OPP and PET films was rubbed by hand rubbing, and the rubbing resistance was evaluated by the number of times until the ink layer was peeled off. ◎ 20 times or more ○ 10 or more to less than 20 times △ 5 or more to less than 10 times × less than 5 times

5) Evaluation of color development The color development of the ink layer on the PET film was evaluated for density, gloss,
Overall evaluation was made by visual observation from the viewpoint of transparency. ◎ Very good ○ Good △ Normal × Poor

Comparative Example 1 3 equipped with a reflux cooling pipe, a nitrogen introduction pipe, a stirrer, and a thermometer
Purging a 1000 ml flask of vine with dry nitrogen, (a
1) as number average molecular weight about 2,000 (hydroxyl value 56)
53 parts of polytetramethylene glycol, 10 parts of dimethylolpropionic acid as (a2), and 4 parts of polyethylene glycol having a number average molecular weight of 2,000 (hydroxyl value 56), and heated to 160 ° C. to be in a transparent state. did.
Under stirring at the same temperature, 29 parts of isophorone diisocyanate was added, and after the addition, the temperature was raised to 190 ° C., and after the temperature was raised, the mixture was reacted for 20 minutes to obtain a polyurethane having an isocyanate group. Next, the temperature was lowered to 160 ° C, and hexamethylenediamine 4 was added.
After the addition, the temperature was raised again to 190 ° C. to obtain an extremely highly viscous polyurethane polyurea polyurea (C2) having a number average molecular weight of about 12,000. Next, 300 parts of distilled water containing 5 parts of ammonia water was added while cooling, and the solid content was about 2 parts.
An aqueous dispersion of 4% by weight of polyurethane polyurea (C2) was obtained. The dispersibility and storage stability of the obtained dispersion were evaluated in the same manner as in Example 1, and the adhesion and the like were evaluated in the same manner as in Example 2. The results are shown in Table 1.

Comparative Example 2 The mixture of polytetramethylene glycol and dimethylolbutanoic acid used in Example 1 was heated to 160 ° C. and made uniform, and then cooled to 100 ° C. Next, under stirring at the same temperature, the entire amount of the urea compound obtained above was added over 10 minutes, and the reaction was continued at the same temperature until the isocyanate group disappeared to obtain a polyurethane polyurea (C3) having a number average molecular weight of about 11,000. Next, 300 parts of distilled water containing 6 parts of aqueous ammonia was added thereto while cooling to obtain an aqueous dispersion of polyurethane polyurea (C3) having a solid content of about 24% by weight. Dispersibility of the obtained dispersion in the same manner as in Example 1,
The storage stability was evaluated in the same manner as in Example 2 and the adhesion was evaluated. The results are shown in Table 1.

[0045]

[Table 1]

[0046]

According to the present invention, a polyurethane polyurea which can be made water-soluble and which can form an ink coating film or the like having high water resistance and good adhesion to a substrate can be prepared without a step of removing an organic solvent. You can now get to. Since the step of removing the organic solvent can be omitted, a polyurethane polyurea which is excellent not only in productivity but also in cost can be obtained. Further, the polyurethane polyurea obtained by the present invention can form a coating film having excellent adhesion to a substrate, abrasion resistance, solvent resistance, and impact resistance. The present invention is useful for aqueous printing inks, and the present invention makes it possible to provide aqueous printing inks having extremely high practical utility.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // C08L 75:00 (72) Inventor Norihito Niwa 2-13-13 Kyobashi, Chuo-ku, Tokyo Toyo Inn Ki Manufacturing Co., Ltd.

Claims (7)

[Claims] 1. A method for preparing an ethylene oxide chain represented by the following general formula (1) without using a diol (a1) other than polyethylene glycol and a polyol (A) containing a diol (a2) having an ionizable dissociating group in the absence of a solvent. Having diamine compound and diisocyanate compound (b1)
Is reacted with a urea compound (B) having an isocyanate group at 130 to 220 ° C. under the condition of excess diisocyanate compound (b1). General formula (1) H ₂ N—R— (OCH ₂ CH ₂ ) _n —O—R′—NH ₂ (wherein R and R ′ are each independently an alkylene group having 1 to 7 carbon atoms; n is an integer of 1 to 500.) 2. The method for producing a polyurethane polyurea according to claim 1, wherein the diol (a1) other than polyethylene glycol contains 1,4-cyclohexanedimethanol and / or polytetramethylene glycol. 3. A polyurethane polyurea obtained from the production method according to claim 1. 4. An aqueous solution or dispersion of a polyurethane polyurea, wherein the polyurethane polyurea according to claim 3 is dissolved or dispersed in an aqueous medium. 5. The aqueous solution or dispersion of polyurethane polyurea according to claim 4, wherein the aqueous medium is an organic solvent having a hydroxyl group and water. 6. The aqueous solution or dispersion of polyurethane polyurea according to claim 5, wherein the organic solvent having a hydroxyl group is selected from the group consisting of isopropyl alcohol, n-butyl alcohol and ter-butyl alcohol. 7. An aqueous printing ink comprising an aqueous solution or dispersion of the polyurethane polyurea according to claim 4.