JPH11158246A - Water urethane polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonionic polymer which shows an excellent whether resistance and thermal resistance and enables preparation of a low viscous, stable and easily handleable aqueous solution by making an aliphatic polyisocyante react with a polyether monool having a specific structure. SOLUTION: An aliphatic polyisocyanate, preferably 2,5-and/or 2,6- diisocyanatomethylbicyclo[2,2,1] heptane is made to react with a polyether monool represented by the formula (wherein R1 is H or methyl group; R2 is a 1-8C hydrocarbon group; and (n) is not less than 3) such that a ratio of NCO group contained in the aliphatic polyisocyanate to OH group contained in the polyether monool (NCO group/OH group) is 0.5-0.4 to produce a water urethane polymer. This water urethane polymer is useful as a new material for a resin, and adhesive or the like particularly for a treating agent for paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aqueous urethane polymer. The aqueous urethane polymer of the present invention can be used as a resin, an adhesive, and other raw materials, including a fiber processing agent, and is extremely useful as a paper processing agent.

[0002]

2. Description of the Related Art Aqueous polyurethanes are classified into aqueous solutions, colloidal dispersions, and emulsions according to their use forms. In addition, if classified according to the method of making water-based, a method using an emulsifier and a method not using this (self-emulsification) can be broadly classified. Divided into ionic. These various water-based polyurethanes are used in resins, adhesives, paints, fiber processing agents, and the like, depending on their characteristics. In recent years, formalin-based resins such as melamine-formalin and urea-formalin have been used for a wide range of applications, as the health hazards caused by formalin have recently become a serious problem. Due to the increasing activity, aqueous urethanes suitable for various applications have been developed.

The nonionic aqueous urethane polymer has the characteristic that it can be used neutrally without using auxiliary materials such as an emulsifier and a neutralizing agent among aqueous urethanes. (Eg, "Polyurethane Resin Handbook" (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun,
1987) pp. 494-507). These are usually
It can be obtained by reacting an organic polyisocyanate with a difunctional or more functional polyol having hydrophilicity. The molecular weight of the organic polyisocyanate depends on the ratio of the organic polyisocyanate to the polyol and the number of functional groups (participating in the reaction). Number of groups to be used). The actual molecular weight varies depending on the purpose used, but ranges from several thousand to several hundred thousand.

[0004] However, when an aqueous urethane is produced by using a bifunctional or higher functional polyol or the like, the molecular weight increases, the viscosity of an aqueous liquid increases, and a sufficient concentration (non-volatile content concentration) is obtained. Inconveniences such as the inability to prepare the aqueous liquid and the difficulty in handling occur. In particular, when used for the processing of textile products or fibrous substrates, there is also a problem that the high viscosity reduces the permeability into the fibers, making it impossible to obtain a sufficient processing effect.

[0005] In order to solve these problems, there is a method of producing a product having a relatively small molecular weight by adjusting the ratio of the organic polyisocyanate and the polyol to be used. Is left as an isocyanate group, resulting in poor stability in water, or depending on the hydrophilicity of the polyol or the like, the resulting compound has insufficient water solubility and cannot be made water-soluble unless used in combination with an emulsifier or the like. There is. Conversely, if the polyol is used in excess, the water-solubility and hydrophilicity become too large, resulting in inconveniences such as not being able to obtain the expected physical properties and low fixability when used in fiber processing. On the other hand, when an aromatic isocyanate such as tolylene diisocyanate or diphenylmethane diisocyanate is used as the organic polyisocyanate component, the reactivity with an active hydrogen compound such as a polyol is very good and the synthesis is easy, but the property that the weather resistance is poor is obtained. Had.

[0006] Under such circumstances, it is possible to prepare an aqueous liquid having a low viscosity as an aqueous urethane which can be suitably used for a fiber processing agent and other uses, and the aqueous liquid has good stability and is easy to handle. Thus, a high-performance aqueous urethane having good physical properties such as water resistance and weather resistance after use has been strongly desired.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and includes a fiber processing agent, a resin, an adhesive,
An object of the present invention is to provide a nonionic aqueous urethane polymer which can be used as another raw material and is particularly useful as a paper treating agent.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found that aqueous urethane obtained by reacting an aliphatic isocyanate with a polyether monool having a specific structure is obtained. The polymer was found to be extremely excellent in physical properties and effects for uses such as a fiber processing agent, and the inventors have further studied and reached the present invention.

That is, the present invention relates to (1) an aliphatic polyisocyanate and a compound represented by the formula (1)

Embedded image (In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents a numerical value of 3 or more.)
Wherein the aliphatic isocyanate is 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1]. ] The aqueous urethane polymer according to the above (1), which is heptane.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The aqueous urethane polymer according to the present invention is characterized by reacting an aliphatic polyisocyanate with a polyether monol.

The aliphatic polyisocyanate used in the present invention is not particularly limited as long as it is an aliphatic polyisocyanate having two or more isocyanate groups per molecule, preferably 2 to 4 per molecule. Preferably 1,6-diisocyanatohexane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate),
1,3- and / or 1,4-diisocyanatomethylbenzene (xylylene diisocyanate), 2,5- and / or
Or 2,6-diisocyanatomethylbicyclo [2.2.
1] heptane, 4,4'-diisocyanatodicyclohexylmethane, 1,3-diisocyanato-4-methylcyclohexane and / or 1,3-diisocyanato-2-methylcyclohexane, 1,3- and / or 1,4- One or more aliphatic polyisocyanates selected from the group consisting of diisocyanatomethylcyclohexane, and more preferably 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1]. ] Heptane. Also, aliphatic polyisocyanate is obtained by dimerization (dimerization), trimerization (isocyanuration), and prepolymerized by a polyfunctional compound having 12 or less carbon atoms and having two or more active hydrogen groups. It is preferably used. As the polyfunctional compound having 12 or less carbon atoms and having two or more active hydrogen groups, glycerin, trimethylolpropane, triethanolamine, diethylenetriamine and the like can be exemplified.

The aliphatic polyisocyanate preferably used in the present invention can be produced by known methods. For example, 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1] heptane is disclosed in
Isoamyl acetate and o- described in JP-A-220167.
Using a mixed solvent of dichlorobenzene, 2,5- and / or 2,6-diaminomethylbicyclo [2.2.1] heptane and 2,5- and / or 2,6-diaminomethylbicyclo [2. 2.1] Heptane hydrochloride is obtained
Phosgene is blown at about 2.2 times the theoretical amount at 60 ° C to perform phosgenation. After the reaction is completed, an inert gas is blown to remove phosgene in the system, then the solvent is removed, and the mixture is rectified under reduced pressure. Is done.

In the present invention, the polyether monool to be reacted with the aliphatic polyisocyanate has the formula (1)
[Formula 3]

Embedded image It is a compound represented by these. Here, R ¹ represents hydrogen or a methyl group, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents a numerical value of 3 or more.

R ^{2 of the} polyether monool of the formula (1)
The hydrocarbon group represented by is not particularly limited as long as it is a hydrocarbon group having 1 to 8 carbon atoms, but a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a cyclohexyl group, An aliphatic hydrocarbon group such as -ethylhexyl group; an aromatic hydrocarbon group such as a phenyl group and a tolyl group; and an aromatic hydrocarbon group such as a phenylmethyl group and a 2-phenylethyl group.

Further, the number n of the polyether monool of the formula (1) is a numerical value of 3 or more, preferably 3 or more and 3 or more.
It is a numerical value of 00 or less, more preferably a numerical value of 3 or more and 100 or less. When n is 2 or 1 and is reacted with an aliphatic polyisocyanate, the resulting urethane compound tends to have low water solubility, making it difficult to prepare a satisfactory aqueous liquid. . Also,
When n is too large, the molecular weight of the polyether monol becomes large, the number of OH groups per unit weight decreases, and sufficient reaction activity cannot be obtained in the reaction with the aliphatic polyisocyanate component, or handling becomes difficult. Inconveniences such as slipping may occur. Therefore, the practical number of n is preferably 3 or more and 300 or less, and more preferably 3 or more and 100 or less.

Examples of the polyether monool compound of the formula (1) used in the present invention include triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether and polyethylene glycol monool having a larger number n. Examples thereof include, but are not limited to, ether, polypropylene glycol monoether, polyethylene polypropylene glycol monoether in which an ethylene chain and a propylene chain are mixed, and a mixture thereof.

These polyether monols can be produced by any known method, but generally, ethylene oxide and / or propylene are used starting from an alcohol having a hydrocarbon group having 1 to 8 carbon atoms represented by R ^2. It is produced by a method of polymerizing an oxide. When produced by such a method, a mixture of compounds having different numbers of n is generally obtained, and such a mixture is also suitably used in the present invention.

The aqueous urethane polymer according to the present invention is not particularly limited as long as it is obtained by reacting an aliphatic polyisocyanate with a polyether monool.
Usually, the ratio of the NCO groups contained in the aliphatic polyisocyanate to the OH groups contained in the polyether monol is N
The reaction is carried out at a ratio such that CO group / OH group = 0.5 to 4.0, preferably NCO group / OH group = 0.8 to 2.0. Such reactants vary depending on the ratio of NCO groups to OH groups, the type of aliphatic polyisocyanate, the number of NCO groups per molecule, and the like. Part N
A mixture of a compound in which the CO group is unreacted, an unreacted aliphatic polyisocyanate, and an unreacted polyether monol is obtained. When the NCO group / OH group ratio is less than 0.5,
Unreacted polyether monool increases, and the properties of the obtained reaction product as urethane deteriorate. When the NCO group / OH group ratio exceeds 4.0, the amount of unreacted compounds or unreacted aliphatic polyisocyanates in some of the NCO groups increases, and the obtained reaction product may be used as an aqueous liquid. It is not preferable because it becomes difficult or the stability in water is reduced.

As the reaction method between the aliphatic polyisocyanate and the polyether monool for obtaining the aqueous urethane polymer according to the present invention, a generally known reaction method between a polyisocyanate and a polyol compound is applied. For example, the method can be performed by adding a polyether monool to an aliphatic polyisocyanate or adding an aliphatic polyisocyanate to the polyether monool.

The reaction can be carried out either without solvent or in the presence of a solvent inert to the NCO groups. In the reaction, a catalyst may or may not be used,
When used, an organometallic catalyst such as an organotin catalyst is preferably used. The amount of the catalyst to be used is generally in the range of 0.001 to 5% by weight, preferably 0.01 to 2% by weight, based on the aliphatic polyisocyanate.

The reaction temperature varies depending on the kind of the aliphatic polyisocyanate to be used, the use of a catalyst, and the use of a solvent, but is usually in the range of 0 to 200 ° C, preferably in the range of 40 to 150 ° C. is there.

The aqueous urethane polymer obtained by reacting the aliphatic polyisocyanate with the polyether monool according to the present invention can be obtained by the above-mentioned reaction method or any other method, and the obtained aqueous urethane polymer is As it is, it is suitably used for various uses such as a fiber processing agent, a resin, an adhesive and the like. However, if necessary, an unreacted monomer may be removed and purified by a thin film distillation method, an extraction method, or the like.

The aqueous urethane polymer according to the present invention is excellent in weather resistance and heat resistance, is capable of preparing an aqueous liquid having a low viscosity, and has a high performance that the aqueous liquid has good stability and is easy to handle. And can be suitably used for fiber processing agents and other uses.

[0024]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. still,
GPC (gel permeation chromatography) measurement of the generated aqueous urethane polymer was performed using Finepak GEL 101F manufactured by JASCO Corporation as a column.
The measurement was carried out using an LC-10A manufactured by Shimadzu Corporation connected to a computer, and the IR measurement was performed using an IR-70 manufactured by JASCO Corporation.
0 was used.

Example 1 A mixture of 2,5- and 2,6-diisocyanatomethylbicyclo [2.2.1] heptane (hereinafter NB) was placed in a 1-liter flask equipped with a thermometer, a dropping funnel and a stirrer.
78.5 g (0.38 mol) was added, and the temperature was raised to 120 ° C. while stirring. Here, polyethylene glycol monomethyl ether (average molecular weight: 550, trade name: UNIOX M-550 (manufactured by NOF Corporation))
421.5 g (0.77 mol) was added dropwise over 1 hour,
After completion of dropping, the mixture was stirred at 120 ° C for 2 hours,
The reaction was carried out at 2 ° C. for 2 hours to obtain a urethane polymer. After the reaction was completed, the NCO concentration was measured according to a conventional method.
% Or less. The obtained urethane polymer is a colorless and transparent liquid, and its viscosity at 25 ° C. is 185 mPa · s.
Met. 1 and 2 show an IR chart and a GPC chart of the obtained urethane polymer. When 5 g of this urethane polymer and 95 g of distilled water were mixed to prepare a 5% aqueous solution, the aqueous solution became a uniform transparent solution, and its viscosity at 25 ° C. was 3 mPa · s. When this 5% aqueous solution was stored at room temperature, 30%
It was stable without any change for more than a day.

Example 2 Polyethylene glycol monomethyl ether was added to 522.
The reaction was carried out in the same manner as in Example 1 except that 5 g (0.95 mol) was used to obtain a urethane polymer. The obtained urethane polymer is a colorless and transparent liquid,
Is 153 mPa · s, and the NCO concentration is 0.1 mPa · s.
It was less than 1%. When 5 g of this urethane polymer and 95 g of distilled water were mixed to prepare a 5% aqueous solution, the aqueous solution became a uniform transparent solution, and its viscosity at 25 ° C. was 3 mPa · s.

Example 3 In a 1-liter flask equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer, 20.6 g of NBDI (0.
10 mol), 0.03 g of dibutyltin dilaurate, and 120 g of acetone were added, and the temperature was raised to 60 ° C. while stirring to bring acetone into a state of gentle reflux. A solution prepared by dissolving 400.0 g (0.20 mol) of polyethylene glycol monomethyl ether (average molecular weight: 2000, trade name: UNIOX M-2000 (manufactured by NOF CORPORATION)) in 200 g of acetone was taken over 1 hour. After completion of the dropwise addition, the mixture is further stirred under reflux with acetone for 3 hours.
Allowed to react for hours. After completion of the reaction, acetone was distilled off under reduced pressure using a rotary evaporator to obtain a urethane polymer. The obtained urethane polymer was a colorless viscous liquid, and its NCO concentration was 0.1% or less. When 5 g of this urethane polymer and 95 g of distilled water were mixed to prepare an aqueous liquid having a concentration of 5%, the aqueous liquid became a uniform transparent solution, and its viscosity at 25 ° C. was 5 mPa · s. When this 5% aqueous solution was stored at room temperature, 30%
It was stable without any change for more than a day.

Example 4 Instead of polyethylene glycol monomethyl ether, polyethylene polypropylene glycol monomethyl ether (average molecular weight: 750, trade name: UNIOX M-
750i (manufactured by NOF Corporation) 135.5 g (0.
The reaction was carried out in the same manner as in Example 3 except that 18 mol) was used to prepare a urethane polymer. The obtained urethane polymer is a colorless and transparent liquid, has a viscosity at 25 ° C. of 241 mPa · s, and has an NCO concentration of 0.3%.
Met. When 5 g of this urethane polymer and 95 g of distilled water were mixed to prepare a 5% aqueous solution, the aqueous solution became a uniform transparent solution and had a viscosity at 25 ° C. of 3 mP.
a · s. When this 5% aqueous solution was stored at room temperature, it was stable without any change for 30 days or more.

Example 5 Instead of NBDI, 1,6-diisocyanatohexane 6
The reaction was carried out in the same manner as in Example 1 except that 7.2 g (0.40 mol) was used to prepare a urethane polymer. The resulting urethane polymer was a white solid at room temperature and had an NCO concentration of 0.2%.

Comparative Example 1 (number of n in polyether monool is less than 3) 24.0 g of diethylene glycol monomethyl ether instead of polyethylene glycol monomethyl ether
The reaction was carried out in the same manner as in Example 3 except that (0.20 mol) was used to obtain a urethane compound. The obtained urethane compound is solid, and its NCO concentration is 0.1%.
It was below. 5 g of this urethane compound and 95 g of distilled water
Were mixed to prepare an aqueous liquid having a concentration of 5%, but the urethane compound was not completely dissolved, and a uniform aqueous liquid could not be obtained.

[0031] 5% strength aqueous solution of an aqueous urethane polymer obtained in Reference Example (Example of use as a paper processing agent in the aqueous urethane polymer) Example 1 was placed in flat containers, non having a basis weight of 80 g / m ² here Test paper obtained by cutting the processed base paper into an A4 size plate was immersed for 2 minutes to impregnate the aqueous urethane polymer solution. Next, the paper was taken out, placed on a square filter paper to absorb excess solution attached to the surface, and dried in a drier at 105 ° C. for 10 minutes in a hanging system. After the humidity control, the weight of the paper was measured, and it was found that the aqueous urethane polymer was impregnated with 2.4 g / m ² . The aqueous urethane polymer-impregnated paper thus obtained and a paper blank-tested with distilled water are prepared, and immersed in distilled water at 20 ° C. for 10 minutes for dimensional stability when wet (elongation in water = length when wet) (Elongation of dryness / length when dry x 100 (%))
Was measured. As a result, the underwater elongation of the blank test paper was 1.65.
%, Whereas the water-based urethane polymer-impregnated paper had an underwater elongation of 1.18%, and an effect of suppressing elongation in water of about 30% was obtained.

[0032]

According to the present invention, weather resistance and heat resistance are excellent.
It is possible to prepare a low-viscosity aqueous liquid, and it has a high performance that the aqueous liquid has good stability and is easy to handle, and an aqueous urethane polymer that can be suitably used for a fiber processing agent and other uses. Provided.

[Brief description of the drawings]

FIG. 1 shows the IR of a urethane polymer obtained by the method of Example 1.
It is a chart.

FIG. 2 shows the GP of urethane polymer obtained by the method of Example 1.
It is a C chart.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoki Sato 30 Mitsui Chemicals Co., Ltd., Asamuta-cho, Omuta-shi, Fukuoka

Claims (2)

[Claims] 1. An aliphatic polyisocyanate having the formula (1)
[Chemical 1] [Chemical 1] (In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents a numerical value of 3 or more.)
An aqueous urethane polymer obtained by reacting with a polyether monool represented by the following formula: 2. The method according to claim 1, wherein the aliphatic isocyanate is 2,5- and / or
Or 2,6-diisocyanatomethylbicyclo [2.2.
1] The aqueous urethane polymer according to claim 1, which is heptane.