JPH02102225A - Water-soluble resin - Google Patents

Abstract

PURPOSE:To obtain the tittle resin soluble in water and org. solvents, having a low softening point and exhibiting no blocking even at high temp. and high humidity and excellent film-forming properties by reacting a water-soluble polyalkylene oxide with a specified amt. of a polyisocyanate compd. CONSTITUTION:A polymeric compd. is prepd. by reacting 100 pts.wt. water-soluble polyalkylene oxide (A) contg. 2 or more OH groups with an average MW of 6,000 or larger, 0-10 pts.wt. low-molecular compd. (B) having 2 or more active hydrogen groups with an MW of 500 or smaller and 0-30 pts.wt. oligomer contg. 2 or more OH groups with an MW of 1,000-5,000 with a polyisocyanate compd. (D). In this case, the amt. of the component D to be used is 0.03-10wt.% based on the total amt. of the components A, B and C and the molar equivalent of NCO in the component D is smaller than the total molar equivalent of active hydrogen groups in the component A, B and C. A water-soluble resin with a low softening point, exhibiting neither change in solubility in water caused by heat-treatment nor change in pH and having no blocking characteristics even at high temp. and high humidity and excellent film-forming properties can be obtd. by said method.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) The present invention relates to a water-soluble resin useful as a water-soluble film base material.

Conventional technology Water-soluble resins with film-forming ability include polyvinyl alcohol, polyethylene oxide, starch, hydroxyethyl cellulose, carboxymethyl cellulose,
Methylcellulose, pullulan, xanthan gum, alginic acid, etc. are known, but all of these have film-forming properties and
There are problems with film strength, perishability, and other aspects.
As a water-soluble film, its practicality was limited.

For example, the most typical water-soluble film currently on the market is polyvinyl alcohol-based film.
There are disadvantages such as ■high melting point of the resin, ■poor solubility in water due to heat treatment or p change, ■strength decreases due to moisture absorption, and furthermore, it is almost insoluble in organic solvents. , its scope of use is very limited.

The present invention eliminates the drawbacks of the prior art, and is a water-soluble resin with excellent film-forming ability, which has a low softening point and whose solubility in water can be reduced by heat treatment or PL+ change. In addition, it has low hygroscopicity with almost no blocking properties even under high temperature and high humidity conditions, is soluble in organic solvents, and has a fast dissolution rate in water and electrolyte aqueous solutions. Our goal is to provide a highly practical resin that is non-perishable.

In the present invention, it has been found that the above problems can be solved by using high molecular weight polyethylene oxide as a compound having active hydrogen to be reacted with polyisocyanate-1.

The water-soluble resin of the present invention contains [A] 100 parts by weight of a water-soluble polyalkylene oxide having an average molecular weight of 6,000 or more and having two or more hydroxyl groups, [B] a molecular weight having two or more groups having active hydrogen. 0 to 10 parts by weight of a low molecular compound having a molecular weight of 500 or less, and 0 to 3 oligomers having a molecular weight of 1000 to 5000 and having 032 or more hydroxyl groups.
It is obtained by reacting 0 parts by weight with a polyisocyanate compound (CD), and the amount of the component used is
[A), [B] and [C] 0 for the total amount of acid components used
．． The molar equivalent of isocyanate contained in component CD) is as low as 03 to 10%, and the molar equivalent of isocyanate contained in component CD) is [A), [B] and [
It is obtained under the condition that the amount is less than the total molar equivalent of groups having active hydrogen contained in component C).

The resin of the present invention has hydroxyl groups, amino groups,
A water-soluble resin with excellent film-forming ability that has at least one functional group such as a carboxyl group or a sulfone group, has a fast dissolution rate in water and an aqueous electrolyte solution, is soluble in organic solvents, and is non-perishable. J1° The product is always easy to handle.

As component [A) of the present invention, any water-soluble polyethylene oxide having an average molecular weight of 6,000 or more and having two or more hydroxyl groups can be used.
It is preferable to use ethylene oxide homopolymers or copolymers of ethylene oxide and propylene oxide and/or butylene oxide. The polyalkylene oxide may contain other components as long as water solubility is not lost.

[A) The average molecular weight of the polyalkylene oxide component is 6
If it is less than 000, the proportion of the [Δ] acid component in the resin obtained by reacting with the [B] (c) and CD) components will decrease, resulting in a lack of hydrophilicity and a slow dissolution rate of the film.
In addition, the solubility in solvents becomes poor, and precipitation occurs in solutions, and the types of solvents that can be used are reduced, which limits processing methods and makes them impractical. Conversely, if the average molecular weight of the polyalkylene oxide becomes higher than several hundred thousand, the solution viscosity increases and becomes difficult to handle.

Next, as the low molecular compound of component [B], a compound having two or more active hydrogens reactive with an isocyanate group,
For example, ethylene glycol, propylene glycol, 1
．． 4-butanediol, ■, 5-bentanediol, 1
, 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and other diglycols; polyalgylene polyamines such as voluteylene polyamine, polypropylene polyamine, and polybutylene polyamine; ethylene oxide or propylene oxide of the above polyalkylene polyamines; Adducts; and polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol; amino alcohols such as monoethanolamine, jetanolamine, and triethanolamine; N-methyl-NN jetanolamine, ethyl N, N Alkanolamines such as jetanolamine, dimethylethanolamine, and diethylethanolamine; thioglycols such as monothioglycol and thiodiethylene glycol; or other dimethylolpropionic acid, isethionic acid, and sulfonic acid
Roxyethyl terephthalate! -, 3-hydroxypropanesulfonic acid, taurine, and neutralized products of these acid substances with basic substances such as sodium hydroxide, potassium hydroxide, ammonia, lower amines, etc. can be used.

These may be used alone or in combination.

In addition, component [B] has the function of promoting the solubility of the resin in water, and is generally used in a ratio of about 0.1 to 2 parts by weight per 100 parts by weight of component [A]. Preferably, as component [A), the average molecular weight is 50.00
When using polyalkylene oxide with a high molecular weight of 0 or more and 80,000 to 120,000, component [A] alone has a flexible film-forming ability, so component [B] and/or In some cases, the intended purpose can be achieved without using component [C].

As the oligomer of component [C], polyether polyols, polyester polyols, polybutadiene polyols, acrylic polyols and the like are preferably used, and these may be used alone or in combination.

Polyether polyols include homopolymers or copolymers containing monomers such as ethylene oxide, propylene oxide, and tetrahydrofuran, or at least one of the above monomers added to polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritonyl. Polymerized polymers are included, and polyester polyols include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 16-hexanediol, trimethylolpropane,
Linear or branched condensation products obtained by dehydration condensation of polyhydric alcohols such as glycerin and polyhydric carboxylic acids such as adipic acid, succinic acid, phthalic acid, maleic acid, pyromellitic acid, or their anhydrides. These include compounds, ring-opened polymers of cyclic ester compounds, condensates of hydroxy acids, and the like.

These [C] components function to increase the film strength, but as the proportion of their usage increases, there is a risk that the dissolution rate of the resin of the present invention will slow down or that it will not dissolve completely. Generally, the amount used is preferably about 1 to 10 to 2 parts by weight per 100 parts by weight of the Al component. As mentioned above, when a high molecular weight polyalkylene oxide is used as component [A], component [C] may not be included.

Next, the polyisocyanate compound used in the present invention is a compound having two or more isocyanate groups in the same molecule, such as propane diisocyanate, hexane diisocyanate, W-11'-dipropyl ether diisocyanate, etc. Isocyanate, thiodiethyl diisocyanate, 1.3
-dimethylbenzene, W weak'-diisocyanate, 1.
4-dimethylnaphthalene W, W' diisocyana-1
-,2,4-toluene diisocyanate, 1,3-dimethylbenzene-2,4 diisocyanate, naphthalene 1
．． 4-diisocyanate-1., 1.3-cyclohexane diisocyanate, methylene bis(4-cyclohexyl isocyanate) xylylene diisocyanate, triphenylmethane-4,4'4'' trisisocyanate, etc., and trimers of these Polymethylene polyphenylisocyanate (Upjohn Co.) A polyisocyanate compound (coronated) obtained by reacting a low molecular weight polyol such as trimethylolpropane with a number of moles of diisocyanate corresponding to the number of active hydrogens in the polyol. and polyisocyanates.

Furthermore, these mono- and polyisocyanates may be masked with a suitable masking agent (the reaction temperature can be raised above the regeneration temperature during the reaction). The above can also be mixed and subjected to the reaction.

In this reaction, the polyisocyanate compound is generally [
A) ・ [B] ・ [C] 0 for the total amount of components
．． It may be used at a ratio of 0.03% to 10.03%.

The optimum amount used varies depending on the type of reaction composition, but it is usually preferably 0.5% to 3% by weight.

[A) ・ (+3) ・ (C,) component and CD)
The reaction of the components is preferably carried out in an anhydrous state and in an inert gas atmosphere, and usually [A] [C]
Acid component CD) is reacted with polyisocyanate to synthesize a prepolymer of terminal isocyanate, and then reacted with component [B], but a mixture of components [A), [B], and [C] and CD) are reacted. It may be reacted simultaneously with polyisocyanate. These reactions are more effective when carried out in a solvent. The reaction temperature varies depending on the type of reaction composition and the amount of reaction accelerator added, but is preferably 50°C to 150°C.

Solvents used in the present invention include N,N dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylene phosphoramide, tetrahydrofuran, acetonitrile, dioxane, methylene chloride, ethane dichloride, chloroform, Examples include fluoroethylene, perchlorethylene, 1,1.1-) refluorethane, benzene, toluene, xylene, fluorocarbon solvents, methyl ethyl ketone, methyl propyl ketone, dimethyl ketone, ethyl acetate, propyl acetate, butyl acetate, and butyl propionate. . These solvents may be used in the reaction system during resin production or for diluting the product, and may be used alone or in combination depending on the solubility of the resin.

In addition, tertiary amines such as triethylamine, pentamethyldiethylenetriamine, dimethylbenzylamine, tetramethyldipropylamine, triethylenediamine, morpholine derivatives, piperazine derivatives, dibutyltin dioctoate, dibutyltin dilaurate, diptyltin diacetate, If a small amount of a reaction accelerator such as triphenyltin acetate or stannath octoate is added, the reaction will proceed more favorably. Furthermore, depending on the purpose, the durability of the resin can be significantly improved by adding, for example, hindered phenol-based, hindered amine-based, sulfur-based, or phosphorus-based antioxidants or light stabilizers to the composition of the present invention. It is possible.

The composition of the present invention is usually produced by reacting each component in a solution form in an appropriate solvent, but it is also possible to produce the composition by dispersing the ingredients or by uniformly mixing the raw materials in powder, solid, or molten form. It can also be obtained by heating and reacting at a predetermined temperature after mixing. Furthermore, in addition to reacting these components in a reaction vessel, each component can be applied as a uniform mixture onto an application substrate and reacted by heating. Because it is soluble or uniformly dispersible in organic solvents, it is possible to remove the solvent with less heat compared to aqueous solutions, making it easy to form coatings, films, etc.
It is possible to form a sheet-like object, and the resin obtained by a solvent-free reaction can be formed into a film or a sheet-like object by an inflation extrusion method, a casting method, or the like.

Examples will be described in detail below, but the present invention is not limited thereto. In the examples, unless otherwise specified, parts and % indicate parts by weight and % by weight.

Further, the dissolution rate test in the Examples was conducted according to the following method.

--Also, each composition was diluted with an appropriate solvent and poured onto a Teflon plate.
Form a uniform layer using a bar coater and dry in a blower oven at 80°C until a constant weight is reached (about 3 hours).
．． A 1 mm dry film is made and cut into 1 cm squares to be used as test pieces.

Separately, 200m j! Solvent for dissolution test (
Distilled water, artificial seawater or organic solvent) 200+wJ! and stir gently using a magnetic cooler at 25°C. The above test piece is placed in this solvent using a pinscent, and submerged with care so as not to adhere to the glass surface or expose the solvent surface, and the time until the test piece becomes transparent and dissolved is measured.

The average value measured five times is shown as the test result.

Example [1] 50 parts of polyethylene oxide with an average molecular weight of 50,000 and 2 parts of polypropylene glycol with an average molecular weight of 2,000, each dehydrated by vacuum drying per minute, were added to 500 parts of acetonitrile, and the mixture was placed in a nitrogen atmosphere. Middle school 30~
After completely dissolving at 40°C, 0.1 part of triethylenediamine was added as a catalyst to this solution, followed by 0.6 part of tolylene diisocyanate, and the mixture was reacted at 70°C for 3 hours. The isocyanate value (hereinafter referred to as
After confirming that the measured value reached the calculated value or less, 0.2 part of triethanolamine was added and the reaction was further carried out at the same temperature for 2 hours.

Thereafter, based on the isocyanate group, infrared absorption spectroscopy (hereinafter referred to as IR spectrum) shows <2250
It was confirmed that the absorption of cm − ' had disappeared, and a water-soluble resin was obtained in the form of a uniform solution. A solubility rate test was performed using the resin solution at 10% solids according to the method described above. The results are listed in Table 1.

Example [2] 40 parts of polyethylene oxide with an average molecular weight of ioo and ooo, each sufficiently dehydrated by vacuum drying, and a polyethylene oxide polypropylene oxide with an average molecular weight of 20,000 and a polyethylene oxide content of 80%. 10 parts of polymer, average molecular weight 2 consisting of ethylene glycol, diethylene glycol and adipic acid
,000 polyester diol was added to 500 parts of trichlorethylene and heated at 30-40°C in a nitrogen atmosphere.
After completely dissolving at 70°C, 0.1 part of triethylenediamine was added as a catalyst, then 1-0.37 parts of hexamethylene diisocyaner was added, and the mixture was reacted at 70°C for 3 hours, followed by a conventional method. After measuring NC0% and confirming that this measured value has reached the theoretical value or less, add glycerin 0%.
．． After adding 1 part of I
<2250c based on isocyanate groups in R spectrum
It was confirmed that the absorption of m-' had disappeared, and a water-soluble resin was obtained in the form of a uniform solution.

Using this resin, a dissolution rate test similar to that in Example [1] was conducted. The results are listed in Table 1.

Example [3] Average molecules sufficiently dehydrated by vacuum drying!
30 parts of polyethylene oxide with an average molecular weight of 50,000, 20 parts of polyethylene oxide with an average molecular weight of 100,000, and 2 parts of polybutylene oxide with an average molecular weight of 4,000,
0.35 parts of dimethylolpropionic acid was added to 500 parts of dimethylacetamide, completely dissolved at 30 to 40°C in a nitrogen atmosphere, and then neutralized with an equivalent amount of triethylamine.
1.05 parts of dibutyltin diacetate and 0.45 parts of xylylene diisocyanate were added to give 70 parts.
After reacting at °C for 5 hours, it was confirmed by IR spectrum that absorption at <2250 cm based on isocyanate groups had disappeared, and a water-soluble resin was obtained in the form of a homogeneous solution.

Using this resin, a dissolution rate test similar to that in Example [1] was conducted. The results are listed in Table 1.

Example [4] 40 parts of polyethylene oxide with an average molecular weight of 50,000 and an average molecular weight of 100 containing 80% polyethylene oxide
10 parts of polyethylene oxide-polypropylene oxide copolymer No. 00 and 1.8 parts of ethylene oxide and 1-cytoadduct of trimethylolpropane (average molecular weight 3,000) were each sufficiently dehydrated by drying under reduced pressure. After that, it was added to 500 parts of tetrahydrofuran and completely dissolved at 30 to 40°C in a nitrogen atmosphere, and then 0.2 parts of dimethylhensylamine and 0.9 parts of isophorone diisocyanate were added and dissolved at 70°C for 30 minutes. After performing the reaction for a certain period of time, measure NC0% by a conventional method, and after confirming that this measured value has reached the theoretical value or less, N-methyl-N
, 0.5 part of N-jetanolamine was added, and the reaction was further carried out for 2 hours at the same temperature, and it was confirmed by the IR spectrum that the absorption of <2250c+n-' based on the isocyanate-1 group had disappeared. A water-soluble resin was obtained in the form of a uniform solution.

Using this resin, a dissolution rate test similar to that in Example [1] was conducted. The results are listed in Table 1.

Example [5] 100 parts of polyethylene oxide having an average molecular weight of 100,000, which had been sufficiently dehydrated by vacuum drying, was added to 500 parts of trichlorethylene, and
After completely dissolving at 0 to 40°C, 0.1 part of 1-lyethylenediamine was added as a catalyst, and 0.16 part of hexamethylene diisocyanate was further added and reacted at 70°C for 5 hours. A water-soluble resin was obtained in the form of a uniform solution. Using this resin, a dissolution rate test similar to that in Example [1] was conducted. The results are shown in Table 1.

Example [6] 50 parts of an ethylene oxide-propylene oxide copolymer with an average molecular weight of 20,000 and a propylene oxide unit component of 10%, and an average molecular weight of 4.000
Two parts of a polyester diol consisting of adipic acid-1,4 to butanediol were each thoroughly dehydrated by drying under reduced pressure, and then added to and dissolved in 1,500 parts of dimethylacetamide. This solution was then neutralized with an equivalent amount of triethylamine. After adding 0.7 parts of sulfonated dihydroxyethyl terephthalate, further adding 0.3 parts of triethylene diamine and 1 part of diphenylmethane diisocyanate, and carrying out the reaction at 70°C for 5 hours, the IR spectrum showed that It was confirmed that the absorption of <2250 parts m-' had disappeared, and a water-soluble resin was obtained in the form of a homogeneous solution.

Using this resin, a dissolution rate test similar to that in Example [11] was conducted. The results are listed in Table 1.

Example [7] 50 parts of polyethylene oxide with an average molecular weight of about 50,000 that was sufficiently dehydrated under reduced pressure and 50 parts of polyethylene oxide with an average molecular weight of 2,000
1 part of polylactone was added to 500 parts of toluene and dissolved at 40°C in a nitrogen stream, followed by 0.05 part of dibutyltin dilaurate and 0.4 part of 1,3-dimethylpenzole 2,4-diisocyanate. was added and reacted at 80°C for 3 hours, then the NC0% was measured using a conventional method. After confirming that this measured value had reached the theoretical value or less, 0.2 part of trimethylolpropane was added and the same reaction was carried out. After reacting for another 2 hours at this temperature, it was confirmed by IR spectrum that the absorption at <2250 cm-' based on isocyanate groups had disappeared, and the resulting resin solution was poured into 4500 parts of n-hexane. , a resin precipitate was obtained.

This precipitate was dried under reduced pressure at room temperature to obtain a slightly yellow powdered resin that was well soluble in water. Furthermore, this resin was uniformly dissolved in trichlorethylene, and a dissolution rate test was conducted in the same manner as in Example [1]. The results are shown in Table 1.

Comparative Example [1] Commercially available polyvinyl alcohol (aging degree 86.5-89%
) was dissolved into a 10% solution with distilled water, and using this solution, a dissolution rate test was conducted in the same manner as in Example (1). The results are shown in Table 1.

Comparative example [2] 10% commercially available hydroxyethyl cellulose with distilled water
It was dissolved in a solution, and using this solution, a dissolution rate test was conducted in the same manner as in Example [1].

The results are shown in Table 1.

Comparative Example [3] A commercially available polyacrylic acid resin was dissolved into a 5% solution using distilled water, and using this solution, a dissolution rate test was conducted in the same manner as in Example (1). The results are shown in Table 1.

Table 1 [Note 1] In the solubility measurement, the case where insoluble materials are not dissolved in 300 seconds is expressed as 〉300.

Effects of the Invention The resin of the present invention can be used in both water and organic solvents, has a relatively low softening point, has excellent film-forming ability, and is very easy to handle.

Furthermore, the resin of the present invention has the advantage that there is almost no change in solubility in water due to heat treatment or PL+ change, almost no blocking property is observed even under high temperature and high humidity, and there is no perishability. There is also.

As described above, the resin of the present invention is a product with excellent processability and stable film-forming ability, and its dissolution rate in water and aqueous electrolyte solutions is extremely high compared to ordinary water-soluble resins such as polyvinyl alcohol. Because it is quick to clean, it can be used for packaging neutral detergents, disinfectants, dyes, pesticides, poisonous substances, etc.
This can be useful for streamlining the operation of dissolving these drugs in water. Similarly, it can be used as a water-soluble resin in seed tapes, curved surface transfer printing, ceramic binders, water-soluble binders, etc.

Claims (1)

[Claims] [A] A compound with an average molecular weight of 6 having two or more hydroxyl groups
000 or more water-soluble polyalkylene oxide, [B] Molecular weight 50 having two or more groups having active hydrogen.
0 to 10 parts by weight of a low molecular weight compound having a molecular weight of 100 or less, and [C] having 2 or more hydroxyl groups.
A polymer compound obtained by reacting 0 to 30 parts by weight of 0 to 5,000 oligomers with a [D] polyisocyanate compound, wherein the amount of the [D] component used is [A], [B] and [ C] is 0.03 to 10% by weight based on the total amount of component used, and the molar equivalent of isocyanate contained in component [D] is
A water-soluble resin characterized in that the amount is less than the total molar equivalent of groups having active hydrogen contained in components [A], [B], and [C].