JPS5910370B2 - Method for producing curable polymer aqueous solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an aqueous curable polymer solution.

Conventionally, resin liquids used in the fields of adhesives, fiber finishing agents, paints, etc. are broadly classified into organic solvent-based ones and water-based ones.

The former organic solvent-based resin liquid generally forms a film quickly;
In addition, the produced film has excellent water resistance, and when used as a paint, the film has advantages such as excellent gloss, but on the other hand, it has disadvantages in terms of public health such as deterioration of the working environment and air pollution. Due to the large amount of water used, its use is gradually decreasing.

On the other hand, the latter water-based resin liquid includes thermosetting resin liquids such as urea resin, melamine resin, and cyclic urea type resin;
Thermoplastic resin emulsions such as vinyl acetate emulsions, acrylic emulsions, synthetic rubber latex, polyvinyl alcohol, water-soluble acrylic resins, polyacrylamide, vinyl acetate-maleic anhydride copolymers, carboxymethyl cellulose, methyl cellulose,
Aqueous solutions of water-soluble 15-polymers such as starch, intermediate epoxy resins,
There are emulsions of thermosetting resins such as urethane resins, but although there are slight differences, all thermosetting resin liquids contain formaldehyde, which causes odor during use and products treated with these. In other words, the release of formaldehyde from plywood, woodwork, and textile products finished using these materials has become a social problem and is subject to regulations, and has serious defects.

In addition, (mouth), ←→, the resin liquid has the advantage of not containing pollution sources such as organic solvents and formaldehyde, but Wataru's thermoplastic resin emulsion and ←→'s water-soluble polymer aqueous solution will be used in the future. The resulting film has drawbacks of insufficient water resistance and low heat resistance. For this reason, some of these resins have thermosetting functional groups introduced into them, but
I haven't found anything that satisfies me. Furthermore, the thermosetting resin emulsion therein is generally unstable and has insufficient practical performance. The present invention provides a method that overcomes these drawbacks and makes it possible to obtain a curable aqueous solution of a polymer, which is insoluble in water but soluble in an alkaline aqueous solution in an aqueous solvent. One or more ethylenically unsaturated monomers that give a polymer that is soluble are polymerized in the presence of an epoxy compound having two or more epoxy groups in one molecule, and if necessary, The present invention relates to a method for producing an aqueous curable polymer solution, characterized in that an alkali is added.

To explain this, it is possible to easily form a uniform, stable, transparent, and glossy continuous film from a curable polymer aqueous solution (hereinafter referred to as "resin liquid") obtained by the method of the present invention described above. In addition, this polymer has good adhesion to various substances, and is crosslinked and cured by drying or heating at room temperature, so it has excellent water resistance,
Heat resistance is excellent.

To discuss these points in more detail, among the conventionally known aqueous resin solutions, the aqueous solution of the water-soluble polymer described in (c) above forms a truly uniform continuous film; Ideally, it would be water resistant.

Substances that can impart such water resistance include ammonium salts of copolymers of acrylic ester and acrylic acid;
Polymers containing both a water-insoluble part and a carboxylic acid ammonium salt part in the molecule, such as the ammonium salt of a copolymer of vinyl acetate and crotonic acid, are known, and these are soluble in water as they are. However, it loses ammonia when it dries to form a film, making it water-insoluble. However, since these are thermoplastic polymers,
It is difficult to avoid softening due to heat, and the water resistance is not truly satisfactory. However, the present inventors have found that when polymerizing these polymers, when a compound having two or more epoxy groups is present in the molecule, the water resistance and heat resistance of the resulting polymer are significantly improved. I discovered that it can be done. Originally, epoxy groups have reactivity with carboxyl groups, ammonia, alkali hydroxides, etc., so in the presence of epoxy groups, acrylic acid, crotonic acid, etc. When polymerizing a polymerizable carboxylic acid such as maleic acid or using the resulting polymer, if it is treated with an aqueous alkali hydroxide solution or ammonia to form an aqueous resin liquid, it will react with these. It is common knowledge that when the ring is opened to form a resin liquid, it has already lost its reactive activity as an epoxy group, and therefore, the resin liquid prepared in this way has particularly excellent water resistance, heat resistance, etc. Even though it is not expected that there will be any effect, it has been confirmed that it has the above-mentioned excellent effects.

In addition, this epoxy compound is presumed to be bonded to the polymer by chain transfer during polymerization, and even when a water-insoluble epoxy compound is added, the resulting (co)polymer aqueous solution is transparent and is a mere mixture. It has also become clear that the invention is different from the above, and the present invention has been completed. In the present invention, the "ethylenic unsaturated monomer that provides a polymer that is insoluble in water but soluble in aqueous alkaline solution" refers to the above-mentioned dissolution behavior when polymerization (or copolymerization) is completed. It refers not only to ethylenically unsaturated monomers that exhibit a It also includes saturated monomers. Acrylic acid, methacrylic acid and other unsaturated carboxylic acids, or their esters or salts are used as the ethylenically unsaturated monomer that provides a polymer that is insoluble in water but soluble in aqueous alkaline solutions, and at least one of these is used. Polymers that are insoluble in water and soluble in aqueous alkaline solutions obtained by polymerizing monomers (mixtures) consisting of are polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, octyl polyacrylate, and polyacrylic. Polyacrylic acid esters such as cyclohexyl polyacrylate, glycidyl polyacrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyoctyl methacrylate, polyglycidyl methacrylate, etc. Polymethacrylic acid esters, partial hydrolysates of these mutual copolymers, neutralized products of some or all of them, or monomers of the above-mentioned acrylic acid or methacrylic acid esters and acrylic acid, methacrylic acid, crotonic acid, maleic acid , copolymers with unsaturated organic acids such as fumaric acid and itaconic acid, or their salts, unsaturated organic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid with styrene, ethylene, and propylene. , unsaturated hydrocarbons such as butylene, alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, N-methylol acrylamide Copolymers thereof, salts thereof, and partially hydrolyzed products thereof are exemplified.

Among these (co)polymers, the main ones are copolymers of unsaturated organic acids such as acrylic acid esters, methacrylic acid esters, and acrylic acid, and copolymers of their esters, and vinyl esters. Copolymers with saturated organic acids and unsaturated organic acid esters such as acrylic esters and methacrylic esters are preferred, and among them, vinyl esters of the latter type, particularly vinyl acetate copolymers, are preferred.

Examples of compounds having two or more epoxy groups in the molecule include condensates of epichlorohydrin or methylepichlorohydrin with polyhydric phenols such as bisphenols such as bisphenol A, trisphenols, and tetrakidphenols, resorcinol and epichlorohydrin. or condensates with methyl epichlorohydrin, alicyclic epoxy compounds such as epoxidized products of cyclohexene and synclopentadiene, glycidyl esters of aromatic polybasic acids such as glycidyl terephthalate and glycidyl phthalate, epoxidized products of polybutadiene, novolac resins and epichlorohydrin or methyl Novolac epoxy resins obtained by reaction with epichlorohydrin, timer acid glycidyl ester resins, epichlorohydrin condensates of polyamines or polyamides, as well as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene Glycol, butylene glycol, neopentyl glycol, 1
, 6-hexanediol, and polyglycidyl ethers of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and mannitol.

All of these epoxy compounds are effective for the purpose of the present invention, but bisphenol A diglycidyl ether and its hydrogenated products, ethylene glycol diglycidyl ether, and diethylene glycol diglycidyl ether have a large number of moles of epoxy groups per unit weight. , triethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol glycidyl ether, and the like are preferred.

The amount of these epoxy compounds to be added may be determined depending on the desired properties of the resulting polymer, and is 2 to 50% of the monomer.
Approximately % by weight is preferred. Polymerization or copolymerization is carried out in an aqueous solvent (in water or in a mixture of water and an aqueous phase or a soluble organic solvent), and the polymerization method may be any known method such as solution polymerization, emulsion polymerization, or suspension polymerization. Can be adopted.

Regarding the addition method of compounds having two or more epoxy groups in the molecule, it is best to allow them to coexist in the system from the beginning of polymerization, but in some cases, some or all of them may be added continuously during the polymerization reaction. It is also possible to add it separately or in parts. As the polymerization initiator, any known water-soluble or oil-soluble radical polymerization initiator can be used depending on the polymerization mode.
There are no restrictions on polymerization temperature, pressure, etc. In addition, various known additives such as polymerization degree regulators, plasticizers, PH regulators, antifoaming agents, emulsifiers, protective colloids, etc. can be added to the polymerization system within a range that does not cause any hindrance.

The polymerization reaction proceeds almost normally even when the above-mentioned epoxy compound is added, and yields close to 100% can be easily obtained in emulsion polymerization and suspension polymerization, but if the polymerization yield is low, monomers may be added as appropriate. It may be purified by methods such as expulsion, salting out, and reprecipitation.

The produced (co)polymer may be used as it is, or it may be added directly to the polymerization solution or after separating the polymer and adding water, methanol, ethanol, isopropanol, acetone, methyl acetate, ethyl acetate. , water-miscible organic solvents such as ethylene glycol, glycerin, diethylene glycol, and propylene glycol, alkali hydroxides such as sodium hydroxide and potassium hydroxide, or ammonia, etc. to be used as an aqueous solution or an aqueous solution of 20% by weight or more. . Water and other solvents such as alkalis to be added at this time vary depending on the composition of the polymer and polymerization solution, and are selected so that the polymer can form a good solution. For example, a solution polymerized by adding an epoxy compound to a lower alkyl ester of acrylic acid and ammonium acrylate in a mixed solvent of water and isopropanol can be used as is, or by adding an epoxy compound to an acrylic ester alone and polymerizing it in a water-ethanol system. Solution polymerized products must be partially hydrolyzed using sodium hydroxide or the like. In addition, if an epoxy compound is added to vinyl acetate and acrylic acid or crotonic acid and subjected to emulsion polymerization or suspension polymerization in an aqueous system, the polymer may be added as is or after the polymer is separated by salting out, aqueous ammonia or methanol or the like may be added as the case may be. The decision may be made depending on the individual case, such as adding an organic solvent to dissolve the resin to form a resin solution. 20 weight of water? What is necessary is to form a solution containing the above-mentioned solvent. The resin liquid obtained by the method of the present invention is preferably an aqueous solution, but depending on the composition of the (co)polymer, the desired permeability of the resin liquid, drying speed, etc. It may also be used as a system with the addition of

At this time, as described above, the water content is preferably at least 20% by weight, and in this case, particularly favorable results can be obtained in terms of handling, dilution, odor, etc. of the resin liquid. There are no particular restrictions on the polymer concentration in the resin liquid, but it is usually 5 to 5.
The concentration is preferably 0% by weight, and when used, the concentration is usually about 1 to 30%, although it varies depending on the purpose.

Depending on the purpose, plasticizers, antifoaming agents, penetrants, smoothing agents, antistatic agents, oil agents, thickeners, film forming aids, preservatives, antifungal agents, antirust agents, etc. are added to this resin liquid. There is no problem in adding anything, and in some cases, crosslinking agents, other types of polymer solutions, emulsions, latexes, dyes, fluorescent agents, flame retardants, fragrances, pigments, fillers, etc. may be added.

This resin liquid can be used in a wide variety of applications such as paint vehicles, coating agents, adhesives, binders, fiber finishing agents, fiber processing agents, and paper processing agents.

Next, examples of the present invention will be given.

However, in the following description, all parts indicate parts by weight. Example 1 Into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a dropping load, 40 parts of vinyl acetate, 5 parts of crotonic acid, and Epicote 815 (trade name, bisphenol A dichelicidyl ether, manufactured by Siel Chemical Co., Ltd.) were added. 10 parts of butyraldehyde, 3 parts of Nitsusan Nonion L-6 (polyoxyethylene laurate, HLBl4.9), 1 part of potassium persulfate, and 191 parts of water were added to the jacket of the reactor.
Heated through a temperature of °C.

Once reflux started, 45 parts of vinyl acetate was added dropwise over a period of about 2 hours, and after 2 hours, the internal temperature was raised to 90°C and aged for 1 hour. As a result, a good product with a residual monomer content of 0.2% was obtained. An emulsion was obtained.

Then, after neutralizing this emulsion with sodium carbonate, add 7 parts of 2.8% ammonia water (2 parts to crotonic acid).
When 43 parts of water were added, a pale yellow transparent viscous resin liquid with a solid content of 30% was obtained. Next, the infrared absorption spectrum of the film obtained by forming the film from the above resin liquid showed absorption of epoxy groups, and it was confirmed that the film was in a state of functioning effectively as a functional group. This film was heated at 150℃.
After heating for 3 minutes, the film was immersed in hot water at 60°C, but no change was observed, indicating that the film had good hot water resistance. Comparative Example 1 A resin liquid was obtained in exactly the same manner as in Example 1, except that Epicote 815 was not used.

A film made from this softened and collapsed when immersed in hot water at 60°C. In addition, although Epikote 815 was added to this resin liquid and stirred, it was not possible to mix it uniformly. Example 2 A reactor similar to Example 1 was charged with 30 parts of vinyl acetate, 3 parts of crotonic acid, 10 parts of Epicote 815, 50 parts of isopropyl alcohol, azobisisobutyronitrile, and 100 parts of water. The jacket was heated by passing warm water at 80°C.

Once reflux started, a mixture consisting of 50 parts of vinyl acetate, 2 parts of crotonic acid, and 5 parts of Epicote 815 was added dropwise over about 2 hours to carry out solution polymerization. Then 1 hour 30
After minutes have passed, reduce the jacket temperature to approximately 90℃ (inner temperature approximately 80℃).
The mixture was aged for 2 hours under reflux. At the end of the reflux, 20 parts of the reflux liquid was distilled off, and 10 parts of 28% ammonia water and 10 parts of isopropyl alcohol were added thereto to obtain a resin liquid. A film formed from the above resin solution was heated at 150°C for 3 minutes and then immersed in warm water at 60°C, but no change was observed, indicating that the film had good hot water resistance.

Example 3 In a reactor similar to Example 1, 90 parts of vinyl acetate, 10 parts of Epikote 834 (trade name manufactured by Ciel Chemical Co., Ltd.), 5 parts of benzoyl peroxide, and polyvinyl alcohol (P manufactured by Shin-Etsu Chemical Co., Ltd.) were added.
Charge 1 part of A-18), 4 parts of n-dodecyl mercaptan, and 250 parts of water, and heat to 80°C in the jacket of the reactor.
heated through hot water.

Once reflux started, a mixture of 10 parts of acrylic acid and 50 parts of water was added dropwise over a period of about 3 hours, and after 1 hour and 30 minutes, the jacket temperature was raised to about 95°C (internal temperature of about 9'C). Aged for 1 hour.

As a result, a good suspension polymer was obtained. Next, the produced polymer was collected by filtration and washed, and then 28%
It was dissolved in a mixture consisting of 10 parts of aqueous ammonia, 330 parts of methyl alcohol, and 100 parts of water to obtain a resin liquid.

A film formed from the above resin solution was heated at 150°C for 3 minutes and then immersed in warm water at 60°C, but no change was observed, indicating that the film had good hot water resistance.

Example 4 In a reactor similar to Example 1, 70 parts of vinyl acetate, 7 parts of crotonic acid, and 1 part of ethylene glycol diglycidyl ether were added.
0 parts of potassium persulfate, 2 parts of potassium persulfate, 10 parts of polyvinyl alcohol (using the above-mentioned PA-18), 3 parts of butyraldehyde and 200 parts of water were charged, and heated by passing hot water at 80 DEG C. into the jacket of the reactor.

Once reflux started, a mixture of 20 parts of methyl methacrylate and 3 parts of crotonic acid was added dropwise over a period of about 3 hours, and after 2 hours, the jacket temperature was increased to about 95°C (internal temperature of about 9.5°C).
0° C.) and aged for 2 hours.

A smooth emulsion with a residual monomer content of 0.6% was obtained. Next, the polymer was salted out and washed by adding sodium sulfate, and then dissolved in a mixed solution of 15 parts of 28% aqueous ammonia, 100 parts of methyl alcohol, and 85 parts of water to obtain a resin liquid.

The presence of epoxy groups in the film obtained by forming the film from the above resin liquid was confirmed by infrared absorption spectral analysis as in the above-mentioned Examples.

This film was heated at 150°C for 3 minutes and then immersed in hot water at 60°C, but no change was observed, indicating that the film had good hot water resistance. Example 5 In a reactor similar to Example 1, 45 parts of vinyl acetate, 15 parts of Epicote 815, 5 parts of azobisisobutyronitrile, 100 parts of methyl alcohol and 50 parts of water were charged. ``C's hot water was passed through and heated.

Once reflux started, a mixture of 15 parts of semi-ammonium maleate and 25 parts of ethyl acrylate was added dropwise over a period of about 3 hours, and after 2 hours and 30 minutes, the internal temperature was reduced to about 60°C.
When the mixture was aged for 2 hours and 30 minutes under reflux, a pale yellow transparent viscous resin liquid was obtained with a polymerization rate of 98%.

A film formed from the above resin solution was heated at 150°C for 3 minutes and then immersed in warm water at 60°C, but no change was observed, indicating that the film had good hot water resistance.

Example 6 In a reactor similar to Example 1, 50 parts of vinyl acetate, 10 parts of trimethylolpropane triglycidyl ether, 2 parts of ammonium persulfate, polyvinyl alcohol (using PA-05 manufactured by Shin-Etsu Chemical Co., Ltd.), and Nitsusan Nonion L- 2 parts of 6, 1 part of butyraldehyde, 10 parts of isopropyl alcohol
and 140 parts of water, and put 8 parts into the jacket of the reactor.
It was heated by passing warm water at 0°C.

When reflux starts, ammonium acrylate 10
and 30 parts of ethyl acrylate for about 2 hours.
It took 0 minutes to drip, and after 1 hour and 30 minutes, the jacket temperature was raised to about 90°C (internal temperature about 80°C), and the temperature was increased to 1 hour and 30 minutes.
After aging for 0 minutes, an emulsion-like resin liquid in a semi-dissolved state was obtained.

50 parts of ethyl alcohol was added to this to obtain a clear solution. A film obtained by forming a film from the above resin liquid was heated to 150°C.
After heating for 3 minutes, O was immersed in hot water at 60°C, and no change was observed, indicating that the film had good hot water resistance.

Example 7 In a reactor similar to Example 1, 75 parts of vinyl acetate, 10 parts of Epicote 815, 5 parts of azobisisobutyronitrile, 60 parts of ethyl alcohol, and 40 parts of water were charged, and the jacket of the reactor was charged with 80 parts of vinyl acetate. Heated through warm water at °C.

Once reflux started, 25 parts of methyl methacrylate was added dropwise over about 2 hours, and after 2 hours and 30 minutes, the mixture was aged for 2 hours while refluxing at an internal temperature of about 80°C to obtain a slightly cloudy solution.

Next, while maintaining the internal temperature at 80°C, add 5 parts of sodium hydroxide and 50 parts of water, stir for 30 minutes, and then add 28 parts of water. 7 parts of ammonia water was added to obtain a colorless and transparent resin liquid. A film obtained by forming a film from the above resin liquid was heated to 150°C.
After heating for 3 minutes, the film was immersed in hot water at 60°C, but no change was observed, indicating that the film had good hot water resistance.

Example 8 In a reactor similar to Example 1, 10 n-butyl acrylate was added.
10 parts of ammonium acrylate, 10 parts of propylene glycol diglycidyl ether, 5 parts of azobisisobutyronitrile, 50 parts of isopropyl alcohol and 60 parts of water were charged, and heated by passing hot water at 75°C into a jacket.

When the internal temperature of the reactor reached 70°C, 80 parts of n-butyl acrylate was added dropwise thereto over a period of 3 hours and 30 minutes. After 2 hours and 30 minutes had elapsed, the jacket temperature was raised to about 90° C. (inner temperature about 80° C.) and the mixture was aged under reflux for 2 hours, yielding a slightly yellow transparent resin liquid. A film formed from the above resin solution was heated at 150°C for 3 minutes and then immersed in warm water at 60°C, but no change was observed, indicating that the film had good hot water resistance. Example 9 In a reactor similar to Example 1, 80 parts of vinyl acetate, 8 parts of crotonic acid, 12 parts of Polyfix 301 (trade name, polyamide epichlorohydrin resin, manufactured by Showa Kobunshi Co., Ltd.), 5 parts of benzoyl peroxide, and polyvinyl alcohol ( 1 part of PA-20 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 200 parts of water were charged, and heated by passing hot water at 80°C through the jacket.

Once reflux started, this state was continued for 5 hours.

Next, the jacket temperature was raised to 95°C (inner temperature 90°C) and aged for 2 hours. When 15 parts of 28% aqueous ammonia was added to the suspension polymerization reaction solution thus obtained, a slightly yellow, transparent, and viscous resin solution was obtained. Example 10 In a reactor similar to Example 1, 30 parts of vinyl acetate, 10 parts of crotonic acid, 10 parts of Epicote 815, 5 parts of polyvinyl alcohol (using PA-18), 0.5 part of sodium lauryl sulfate, and phosphorus were added. 2 parts of sodium oxyhydrogen, 1 part of ammonium persulfate, and 200 parts of water were charged, and 80°C hot water was passed through the jacket and heated.

Once reflux started, a mixture of 45 parts of vinyl acetate and 15 parts of N-methylolacrylamide was added dropwise over a period of 2 hours, and after 1 hour and 30 minutes the jacket was heated to 95°C (
The mixture was aged at an internal temperature of 90° C. for 2 hours to obtain a good emulsion.

Next, 7 parts of 28% ammonia water was added to this emulsion to obtain a pale yellow viscous resin liquid. A film (dried at room temperature) obtained by forming the film from the above resin liquid was immersed in warm water at 60°C, but no change was observed, indicating that the film had good resistance to hot water.

Comparative Example 2 A resin liquid was obtained in exactly the same manner as in Example 2, except that Epicote 815 was not used.

The film obtained from this softened and disintegrated when immersed in hot water at 60°C. Also, add Epicoat 8 to this resin liquid.
15 was added, but it could not be mixed uniformly. Comparative Example 3 A resin liquid was obtained in exactly the same manner as in Example 3, except that Epicote 834 was not used.

The film obtained from this softened and disintegrated when immersed in hot water at 60°C. Also, add Epicoat 8 to this resin liquid.
34 was added and stirred to obtain a cloudy emulsion-like resin liquid, but this was unstable and caused sedimentation when left to stand.
℃ warm water test showed little improvement. Comparative example
4 A resin liquid was obtained in exactly the same manner as in Example 5, except that Epicote 815 was not used.

The film obtained from this softened and disintegrated when immersed in hot water at 60°C. Also, add Epicoat 8 to this resin liquid.
15 was added, but it could not be mixed uniformly. Comparative Example 5 A resin liquid was obtained in exactly the same manner as in Example 7, except that Epicote 815 was not used.

Claims (1)

[Claims] 1 In an aqueous medium, one or more ethylenically unsaturated monomers that give a polymer that is insoluble in water but soluble in an aqueous alkali solution are mixed with two or more epoxy monomers in one molecule. A method for producing an aqueous curable polymer solution, which comprises polymerizing in the presence of an epoxy compound having a group, and adding an alkali if necessary.