JPS5927403B2 - Method for producing alcohol-modified melamine resin fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing flame-retardant fibers made of alcohol-modified melamine-aldehyde resins with excellent productivity and fiber quality.

In recent years, flame retardant performance has come to be required for textile products from the standpoint of fire prevention.

Furthermore, even if it were to burn, it would generate less smoke and toxic gases.
Or, it has come to be required that the material does not become molten.

In order to meet such demands, there are limits to the improvement of existing general-purpose fibers, and various new fibers that inherently have flame retardant properties have been developed.

Among these fibers, melamine resin fibers have strength and other useful properties as fibers in addition to flame retardancy, but they have a number of problems in the manufacturing process.

That is, the melamine-aldehyde initial condensate solution, which is a spinning solution, itself has poor stability, and phenomena such as increased viscosity, gelation, and devitrification are observed over time.

This stability varies depending on the degree of alkylolization of the melamine-aldehyde initial condensate, the concentration in the solution, and the retention ring that maintains the pH of the solution at 200, which is the viscosity required for the spinning solution.
In a solution adjusted to exhibit ~2800 poise, either or both of a rapid increase in viscosity and devitrification occur within 10 hours after adjustment, and spinning using this solution causes yarn breakage and uneven fineness. Otherwise, it may become impossible to spin.

Furthermore, since this solution does not have sufficient spinnability, it is extremely difficult to continuously produce uniform filaments industrially.

The inventors conducted extensive research to improve these drawbacks, and as a result they arrived at this invention.

This invention involves etherifying at least 20% of the alkylol groups of a melamine-aldehyde precondensate in the presence of alcohol, and placing the resulting alcohol-modified melamine-aldehyde resin precondensate solution in a fiber-forming atmosphere. Another invention is a method for producing alcohol-modified melamine resin fibers, characterized by spinning out at least 20% of the alkylol groups of a melamine-aldehyde initial condensate in the presence of an alkotyl. A method for producing alcohol-modified melamine resin fibers, which comprises spinning the resulting alcohol-modified melamine-aldehyde resin initial condensate solution into a fiber-forming atmosphere and then heat-treating it at a temperature of 70 to 300°C. be.

The spinning solution mainly composed of an alcohol-modified melamine-aldehyde resin initial condensate of the present invention exhibits extremely superior stability compared to conventional solutions mainly composed of an unalcohol-modified melamine-aldehyde resin initial condensate. In addition, it has been observed that the yarn exhibits significantly superior spinnability, and as a result, it has become possible to form fibers much more easily than with conventional methods.

The melamine-aldehyde resin initial condensate solution used as a spinning solution in the conventional method is composed of several kinds of oligomer compounds, and has poor spinnability by itself, and when extruded through a spinneret, Since it is subjected to shear stress in an uncured state directly under the spinneret, it is extremely easy to break, making it difficult to obtain continuous filaments.

In order to correct these shortcomings, efforts have been made to improve the spinnability by adding a solution-based polymer or boron oxide to the aqueous solution of the melamine-aldehyde resin initial condensate, but this is still insufficient. do not have.

However, as in this invention, the alcohol-modified melamine-aldehyde resin alcohol solution, which is obtained by adding alcohol to the melamine-aldehyde resin initial condensate and subjecting it to a heating reaction, has extremely excellent spinnability by itself, so it is difficult to form fibers through a spinneret. Even when extruded into the atmosphere, there is hardly any breakage of the filament directly under the spinneret.

Furthermore, due to its excellent stringability, the spinning speed can be significantly increased.

Furthermore, the aqueous solution of the melamine-aldehyde resin initial condensate itself has poor stability, and phenomena such as increased viscosity, gelation, and devitrification are observed within several hours.

Therefore, when spinning using this solution, not only will it cause yarn breakage, uneven fineness, or the inability to spin, but the gelation of the spinning solution will cause the needle rod of the spinning solution to
This occurs in transport pipes, spinning machines, or spinnerets, and since the gel produced is stable, it is extremely difficult to remove, and this has seriously hindered industrialization.

However, the alcohol-modified melamine resin alcohol solution of this invention itself has excellent stability, and phenomena such as increased viscosity, gelation, and devitrification are observed even after more than 100 hours at room temperature (25°C). Furthermore, the stringiness is not deteriorated.

Therefore, it enables stable industrial continuous production.

Furthermore, the obtained fibers are characterized by flame retardancy, and have extremely high tensile strength and excellent flexibility compared to fibers obtained from melamine resin cotton hardware.

This invention enables industrial production of alcohol-modified melamine-aldehyde resin fibers to be advantageously advanced.

The alcohol-modified melamine-aldehyde initial condensate used in this invention can be used alone or in combination with a third component such as guanamines such as benzoguanamine and acetoguanamine, guanidine, dicyandiamide, ammeline, phenol, urea, and thiourea. sell.

Examples of aldehydes include formaldehyde, paraformaldehyde, aliphatic aldehydes, aromatic aldehydes, and substituted aldehyde compounds thereof, which may be used alone or in combination.

The melamine-aldehyde initial condensate includes not only N-alkylol melamine but also a condensation of several molecules thereof.

Among the melamine-aldehyde initial condensates, melamine-formaldehyde initial condensates are particularly preferred.

A case will be described below in which N-methylolmelamine is produced by the reaction of melamine and formaldehyde and then converted into alcohol, but the reaction between melamine and other aldehyde compounds can also be carried out in the same manner.

The melamine-formaldehyde initial condensate is prepared by mixing melamine and formaldehyde in a molar ratio of 1:2 to 1:15, preferably 1:3 to 1:8, making an aqueous solution, and preparing it under neutral or slightly alkaline conditions (weak acidity is also acceptable). 3 at 60℃~80℃
Allow to react for 0 minutes or more.

At 80°C or higher, the CH2O removal reaction is promoted and gelation occurs.

Up to 6 moles of formaldehyde can be bound to 1 mole of melamine, but in the melamine-formaldehyde initial condensate used in this invention, substantially 2 to 6 moles of formaldehyde can be bound to 1 mole of melamine. A molar bond is preferred.

A reactant having such a ratio can be obtained by reacting 3 to 8 moles of formaldehyde with 1 mole of melamine.

) The aqueous solution of the ramine-formaldehyde initial condensate obtained by the above method can be used as it is, or can be used after being concentrated or diluted.

In addition, it is also possible to use a powder that has been precipitated and separated from a concentrated solution, or a commercially available N-methylolmelamine powder that is made into an aqueous solution.

At least 20% of the alkalol groups in the alkalol melamine reacted with the melamine and the aldehyde in this invention
is required to be etherified with alcohol, preferably 30% or more, most preferably 50% or more.

If the degree of etherification is less than 20%, the extremely good solution stability and stringability, which are the characteristics of this invention, will not be exhibited.

In order to increase the degree of etherification to 20% or more, it is necessary to add alcohol by a molar ratio of 2 to 15 times that of melamine.

It is possible to add 15 times or more alcohol, but since adding more than this does not contribute to etherification of the alkalol group, the result is that the excess alcohol is simply distilled off in the concentration step, which is wasteful.

If it is less than 2 times, the alcohol denaturation will be insufficient and the stringiness will deteriorate.

In addition, when using an alcohol that phase separates from water such as butanol, the water produced by etherification is azeotropically fixed with the alcohol and removed from the system, and only the alcohol separated by cooling is allowed to flow back into the reaction system. It can accelerate the reaction.

The alcohol used for modification may be added before the melamine-formaldehyde resin initial condensate is synthesized, or may be added during or after the synthesis of the melamine-formaldehyde resin condensate.

An example of an alcohol modification reaction of a melamine-formaldehyde initial condensate is to add alcohol to an aqueous solution of a melamine-formaldehyde initial condensate at a molar ratio of 2.
After adding 0 times or more, preferably 3.0 to 15.0 times, the solution is adjusted to a weak acidity, preferably pH 60 to pH 5,0,
A modification reaction is carried out under reflux for 30 minutes or more, and then water or water and alcohol are distilled off to obtain a spinning solution having a predetermined viscosity.

Alternatively, N-methylolmelamine powder is added to alcohol so that the molar ratio of alcohol to melamine is 2.0 times or more, preferably 3.0 to 15.0 times, and then the denaturation reaction is carried out under weak acidity. I can do things.

The alcohol used in this invention is preferably a primary alcohol having 5 or more carbon atoms.

Specifically, methanol, ethanol, l'l-FD
Panol, Impropatol, n-butanol, imbutanol, 5ec-butanol, t-butanol, n-
Examples include amyl alcohol, iso-amyl alcohol, n-hexanol, cyclohexanol, n-octyl alcohol, benzyl alcohol, methanol, ethanol, n-gropanol, impropanol,
Examples include, but are not limited to, aliphatic alcohols such as n-butanol, 5eC-butanol, and inbutanol.

It is necessary that the spinning solution exhibits the spinnability necessary for spinning.

The stringability of a solution is significantly influenced in particular by the viscosity of the solution.

From the viewpoint of stringability, the rotational viscosity, the viscosity measured by a meter, is preferably in the range of 100 to 100 poise.

Most preferably it is 500 to 5000 poise.

To achieve this viscosity range, either stop the reaction when the viscosity of the initial condensate of alcohol-modified melamine-aldehyde resin falls within this viscosity range, or furthermore, prepare an alcohol solution of the initial condensate of alcohol-modified melamine-aldehyde resin with a viscosity of 1
After concentrating to 0,000 poise or more, it can be diluted with an inert solvent such as methylene dichloride, trichlorethylene, perchlorethylene, etc. to a viscosity of 100 to 100 poise and then used.

When the viscosity is less than 100 poise, stable spinning is impossible due to poor spinnability, and when it is more than 10,000 poise, it is necessary to discharge at high pressure, and furthermore, it becomes difficult to discharge.

The viscosity of the solution is determined by the degree of alkalolization of N-alkarolmelamine, the degree of condensation, the degree of alcohol modification of the alkalol group,
It depends on the type and concentration of alcohol, the type and mixing ratio of additives, and the holding temperature.

In particular, it depends on concentration and holding temperature.

The concentration of the alcohol-modified melamine-aldehyde resin initial condensate is 20% to 80% by weight, preferably 30% by weight.
It is within the range of 70% by weight.

It is preferable to maintain the holding temperature in the range of 10°C to 70°C.

There is a significant difference in stringability between the conventional melamine-aldehyde resin initial condensate and the alcohol-modified melamine-aldehyde resin initial condensate of the present invention even at the same viscosity.

Compared to the initial condensate of melamine-aldehyde resin, the initial condensate of alcohol-modified melamine-aldehyde resin shows a marked improvement in stringiness, but it is also possible to add an alcohol-soluble polymer to further improve the stringiness. can.

The flexibility and strength of alcohol-modified polymers can be improved by adding alcohol-soluble polymers.

Examples of alcohol-soluble polymers include polyvinyl acetate-1-, polyvinyl acetal, polyvinyl butyral, polyvinylpyridine, polyvinylpyrrolidone, polybutyl methacrylate, polyhexyl methacrylate, polyoctyl methacrylate, polymethacrylic acid, cellulose nitrate, methylcellulose, ethylcellulose, Examples include polyethylene glycol.

The alcohol-soluble polymer is mixed and dissolved together with the alcohol-modified melamine-aldehyde resin initial condensate to form a spinning solution.

This mixing may be carried out by adding the alcohol-soluble polymer powder to the alcohol solution of the alcohol-modified melamine-aldehyde resin initial condensate, or by mixing the polymer previously dissolved in alcohol.

Furthermore, among the alcohol-soluble polymers, water-soluble polymers such as polymethacrylic acid, polyvinylpyrrolidone, and polyethylene glycol can be added before the alkalolized melamine synthesis.

The mixing ratio of the alcohol-modified melamine-aldehyde resin initial condensate and the alcohol-soluble polymer varies depending on the type of polymer, its degree of polymerization, the type of alcohol used, and the concentration of the alcohol-modified melamine-aldehyde resin condensate. The amount is in the range of 30% by weight or less based on the initial condensate.

The spinnability and spinnability of the spinning solution are better as the mixing ratio of alcohol-soluble polymer increases, but on the other hand, since alcohol-soluble polymer is flammable, the flame retardance of the fiber decreases as the mixing ratio increases. do.

Therefore, from the viewpoint of flame retardancy, the mixing ratio of the alcohol-soluble polymer is preferably up to 30%.

The spinning solution used in the present invention cures and becomes three-dimensional by heating itself, but the curing speed can be significantly increased by adding an appropriate curing agent.

That is, by adding an acidic substance or a substance capable of producing an acidic substance by thermal decomposition to this alcohol-modified melamine-aldehyde resin initial condensate, the curing speed can be significantly increased.
As a result, the spinning temperature can be lowered by shortening the length of the spinning tube (
Not only are effects such as making the yarn less prone to sagging and yarn breakage, and increasing the spinning yield, but also improvements in yarn physical properties such as strength and elongation of filaments obtained by spinning are observed.

Examples of acidic substances include various organic acids such as formic acid, acetic acid, and oxalic acid.

Examples of substances that can be thermally decomposed to produce acidic substances include ammonium salts of inorganic acids such as ammonium chloride, ammonium sulfate, and ammonium nitrate, ammonium salts of organic acids such as ammonium acetate, formic acid esters, and acid amides.

However, stability is required while it exists as a spinning solution, and it is required to accelerate the curing rate when spun into a fiber-forming atmosphere from a spinneret, so it is rarely used as a curing agent at room temperature. It is preferable to use a latent curing agent such as methyl formate, ethyl formate, formamide, or salicylic acid, which does not exhibit curing properties.

The amount of curing agent added varies depending on the type, but usually about 0.5 to 5% by weight can be used.

If the amount of the hardening agent added is less than 0.5% by weight, the effect will not be sufficiently exhibited, and if the amount is more than 5% by weight, the effect will not only be moderated but the stability of the solution will decrease, which is not preferable.

The curing agent may be added at any time after alcohol denaturation and before spinning, but it is preferably added immediately before spinning in order to maintain the stability of the solution.

The alcohol-modified melamine-aldehyde initial condensate solution obtained as described above may be mixed with various additives as required, or used as it is as a spinning solution.

Examples of additives include matting agents and pigments.

Examples of polishing agents and pigments include titanium dioxide, carbon black, and kaolinite.

Alcohol-modified melamine resin fibers can be obtained by spinning the spinning solution obtained as described above through a spinneret in a fiber-forming atmosphere.

As the spinneret used in this invention, a spinneret conventionally used in dry spinning, wet spinning, etc. is used.

It is preferable to use a spinneret having a hole diameter of 0.1 to 0.7 mmφ.

If the hole diameter is less than 0.1mmφ, the yarn will break easily, and if the hole diameter is more than 0.7mmφ, the fibers to be discharged will be
Because it becomes thick, it is difficult to remove the solvent or it may cause foaming.

Preferably, the temperature of the spinning solution and the temperature of the spinneret are maintained within the range of 10°C to 70°C.

The solution consisting of the initial mesh of alcohol-modified melamine-aldehyde resin is extremely stable, so it remains stable for a considerable period of time even at temperatures above 70°C, but especially when a hardening agent is added, the solution may increase viscosity, harden Three-dimensional formation often occurs, resulting in decreased spinnability or clogging of the pores of the spinneret with cured material, which may lead to deterioration in spinning quality.

Furthermore, if the temperature is as low as 10° C. or less, the fluidity of the solution decreases, which is undesirable.

The most preferred temperature range is 30°C±10°C.

The spinning solution is filtered and defoamed according to conventional methods, and then extruded from a spinneret.

Although wet coagulation can be used as the atmosphere for extruding the spinning solution, dry coagulation is preferable.

That is, the spinning solution is extruded through a spinneret into a heated gas at a temperature of 70° C. or higher, preferably 150° C. or higher, and the spinning is continuously carried out while removing the solvent and performing a curing reaction to obtain alcohol-modified melamine resin fibers. .

The curing reaction in this invention is a condensation reaction including three-dimensionalization by dealcoholization.

The temperature atmosphere depends on the concentration of the initial mesh of alcohol-modified melamine-aldehyde resin, the type of alcohol used, the degree of denaturation,
It varies depending on the type of alcohol-soluble polymer added, the degree of polymerization, the amount added, and the type and amount of curing agent, but it is 70 to 3
The temperature is 50°C, preferably 150 to 330°C.

150 to remove the solvent and perform the curing reaction in a short time.
Temperatures above °C are preferred, but the temperature at the initial stage of extrusion is 7°C.
After removing the solvent at 0℃ or higher and 150℃ or lower
It is also possible to carry out the curing reaction in an atmosphere at temperatures above .degree.

If the ambient temperature is 350° C. or higher, the resulting fibers may foam or become colored, which is not preferable.

The heating gas used in this invention includes inert gases such as nitrogen and helium, air, and water vapor.

The fibers spun as described above can be further subjected to a curing reaction treatment, if necessary, in order to further advance the crosslinking reaction.

As the hardening reaction treatment, heat treatment is usually performed.

The temperature for heat treatment varies depending on the fiber thickness, degree of hardening, heat treatment atmosphere, conditions, and treatment time, but is between 70 and 300℃.
℃, preferably 100 to 250℃.

When the temperature is 70° C. or lower, it takes a long time for the heat treatment effect to appear on the yarn properties, while when the temperature is 350° C. or higher, coloring is observed in the fibers.

Heat treatment time depends on fiber thickness, degree of hardening, heat treatment atmosphere,
Varies depending on temperature and condition.

Heat treatment can be performed at a low temperature for a long time, but it can also be heat treated at a high temperature for a short time.

As the atmosphere for the heat treatment, a heating medium such as air, nitrogen, steam, or hot water, a hot plate, a hot roll, etc. can be used.

Further, the heat treatment can be carried out under no tension or under tension.

Furthermore, when performing such heat treatment, dry heat stretching can be performed in order to improve the toughness of the resulting fiber.

The spun fibers are subsequently heated and stretched by passing through a heating medium at 100° C. or higher or by bringing them into contact with a hot plate or hot roller.

The stretching ratio is 10% or more, preferably 50% or more.

The alcohol-modified melamine resin fiber thus obtained exhibits extremely excellent flame retardancy.

That is, even if it comes into contact with a fire source, its combustion speed is extremely slow, and the amount of smoke generated during combustion is small, and it exhibits self-extinguishing properties when the fire source is moved away.

In addition, it is heat infusible.

Furthermore, the fibers produced by the method of this invention exhibit superior toughness (strength, elongation) and high fiber uniformity compared to melamine fibers produced by conventional methods.

That is, the fibers have less unevenness in fineness and the dyed cloth has fewer unevenness.

It also shows sufficient flexibility and has an extremely good texture.

Furthermore, it has transparency and gloss as a melamine fiber, and also has excellent dyeability and color development, and the dyed fiber also has good light resistance.

The present invention will be described in detail below with reference to Examples.

Example 1 126 parts of melamine, 405 parts of 37% formalin aqueous solution (
Formalin/melamine molar ratio is 115), n-butanol 741 parts (n-butanol/melamine molar ratio is 1)
/10), 25 parts of toluene was added, and after 20 minutes it became 90
The mixture was heated to ℃ and stirred to uniformly dissolve it.

Then 0.5 NHCl was added to bring the pH to 6.0, followed by 5 tark & De at a temperature of 92-95 °C.
Water was extracted for 3 hours using a water separator.

This was further concentrated under reduced pressure at 60° C. for 2 hours to obtain a transparent spinning solution A with a resin concentration of 60%.

The viscosity measured by a B-type rotational viscometer at 25° C. was 2000 poise.

This solution was left in a constant temperature room at 25° C. for 100 hours, but neither devitrification nor gelation was observed, and the viscosity remained unchanged at 2000 poise.

When left for another month, the viscosity increased to 2,900 poise, but no phenomena such as devitrification were observed, and when it was attached to a glass rod and pulled up, it maintained excellent stringability.

Next, the spinning solution A is put into a defoaming tank through a filter,
After being left under reduced pressure (20 mmHg) for a day and night, it was extruded into dry nitrogen at 250°C through a spinneret with 10 pores with a pore diameter of 0.25 mm kept at a temperature of 30°C, and the butanol was evaporated and the butanol-modified melamine-formaldehyde resin was initialized. Curing the condensate, tightening 200m/m1yi
It was rolled up at a speed of .

The spinning condition at that time was extremely good, and no yarn breakage was observed.

The obtained yarn is a colorless and transparent yarn with a single yarn fineness of 5 denier and a strength of 3.5? /d and elongation of 12%, which were extremely excellent.

The uniformity of this yarn was measured with a 1.1% evenness tester and was found to be 1.6%.

When this thread was wrapped around a needle of 1m7rLφ, it showed excellent flexibility.

Furthermore, the knot strength of this yarn was 2.1'/d.

As a result of a combustion test using an oxygen index combustion tester 0N-1 manufactured by Suga Test Instruments, the LOI value was 34.0, and little smoke was emitted during combustion, indicating thermal infusibility.

Furthermore, this fiber is dyed with acid dye Alizarin Light Blue 4GL.
(C, I, 61125), dye concentration 5% owf,
Ammonium acetate 3% owf, pH 3.5, bath ratio 1
: After dyeing at 100°C for 60 minutes under the dyeing conditions of
When absorbance was measured at mμ, the dye adsorption rate was 92%.
It was excellent.

The light fastness of this dyed thread after irradiation with a fetometer for 60 hours was grade 5.

Example 2 126 parts of melamine was added to 649 parts of a 37% formalin aqueous solution (formaldehyde/melamine molar ratio 8/1).
The temperature was raised to 92° C. for 1 hour while heating and stirring.

Next, 593 parts of 5ec-butanol and 25 parts of toluene were added (5ec-butanol/melamine molar ratio 8/1).
) After adding 0.5N hydrochloric acid and adjusting the pH to 6.2, 92~
Water was removed at a temperature of 95° C. using a 5 Tark & Dean water separator for 3 hours and 30 minutes.

This was further concentrated under reduced pressure at 60° C. for 2 hours to obtain spinning solution B with a resin concentration of 70%.

The viscosity measured by a B-type rotational viscometer at 25° C. was 2,800 poise, indicating excellent stringability.

This solution was left in a constant temperature room at 25°C for 100 hours.
No devitrification or gelation phenomena were observed, and the viscosity remained unchanged at 2,800 poise.

When left for another month, the viscosity reached 3,600 poise, but no devitrification or gelation phenomena were observed, and excellent stringability was maintained.

Next, the spinning solution B is passed through a filter and put into a defoaming tank.
After being left for one day and night under a reduced pressure of 20 vuaHg, the temperature was 40°C.
The mixture was extruded into dry nitrogen at 280°C through a spinneret having 10 pores with a pore diameter of 0.25 mm maintained at 250° C. to evaporate the 5ec-butanol and harden the initial condensate of the melamine-formaldehyde resin modified with 5ec-butanol.
It was rolled up at a speed of m/mm.

The spinning condition at that time was extremely good, and no yarn breakage was observed.

The obtained yarn was a colorless and transparent yarn with a single filament fineness of 4 denier, and had an extremely excellent strength of 3.7 P/d and elongation of 11%.

The uniformity of this yarn was measured with a 4% evenness tester and was found to be 1.7%.

When this thread was wound around a 1 mm diameter needle, it showed excellent flexibility.

Furthermore, the knot strength of the yarn was 2.2 P/d.

The LOI value was 33.5, and it exhibited excellent flame retardancy with little smoke emitted during combustion.

Further, the dyeability and light fastness were examined in the same manner as in Example 1, and the dye adsorption rate was 93% and the light fastness was grade 5.

Example 3 126 parts of melamine, 405 parts of 37% formalin aqueous solution (
formalin/melamine molar ratio 5/1), propanol 601 parts (propanol/melamine molar ratio 10/1)
) and 25 parts of l-luene were added and stirred while heating to 90° C. for 20 minutes to uniformly dissolve.

Then, after adding 0.5 NHC1 to bring the pH to 6.0, Stark & Dea was added at a temperature of 92-95°C.
Only water was extracted for 3 hours using a water separator.

This was further concentrated to obtain a transparent spinning solution C with a resin concentration of 50%.

The viscosity measured by a B-type rotational viscometer at 25° C. was 750 poise.

This solution was left in a constant temperature room at 25° C. for 100 hours, but neither devitrification nor gelation was observed, nor was there any change in viscosity.

This solution is then passed through a filter into a defoaming tank and passed through a 2
After being left at 0 mmHg for 12 hours, 2
It was extruded into dry air at 50° C. to evaporate the glopanol and harden the glopanol-modified melamine-formaldehyde resin initial condensate, and then it was rolled up at a speed of 180 m 2 /mul.

The spinning condition at that time was extremely good, and no yarn breakage was observed.

The obtained yarn is a colorless and transparent glossy yarn with a single fiber of 6 denier and a strength of 3.2'? /d, elongation 15%, knot strength 1.7? /d, which was extremely excellent.

The uniformity of this yarn was 1.7%, and it showed excellent flexibility even in a winding test on a 1 mmφ wire.

Furthermore, the LOI value in the combustion test was 33.5.

Moreover, there was less smoke.

The dyeing rate of Alizarin Light Blue 4GL at 100°C for 60 minutes was 93%, and the dyeing rate was 93%.
The light fastness after irradiation for 0 hours was grade 5.

Example 4 126 parts of melamine, 405 parts of 37% formalin aqueous solution (
formalin/melamine molar ratio 5/1), butanol 4
00 parts (butanol/melamine molar ratio 5.4/I-)
was charged into a reactor, adjusted to pH 6.2 with ammonia, and adjusted to 9.
Melamine was dissolved at 8°C and methylolation reaction was carried out for about 30 minutes, and a small amount of butyl phosphoric acid ester was added.
The butylation reaction was carried out for about 1 hour.

Meanwhile, 50 parts of xylene was added to promote dehydration.

The obtained reaction solution was concentrated under reduced pressure at 60°C for 3 hours,
A transparent spinning solution with a resin concentration of 80% was obtained.

The viscosity measured by a B-type rotational viscometer at 25°C was 5,000 poise, and the solution was stable even when left at 25°C for 100 hours.

Next, the spinning solution was passed through a filter into a degassing tank, left under reduced pressure (20 mmHg) day and night, and passed through a spinneret with 12 pores with a pore size of 0.20 mm maintained at a temperature of 60°C in dry heated air at 280°C. Extruded to 230 m/
It was rolled up at a speed of min.

The spinning condition was extremely good, and no yarn breakage was observed.

The obtained yarn is a colorless and transparent glossy yarn with a single yarn fineness of 4 denier and a strength of 3.8'i? /d, elongation of 10%, knot strength of 2.1'/d, and uniformity of 1.4%, which were extremely excellent.

Further, this yarn showed an LOI value of 34.5, a dyeing rate of 92% in Alizarin Light Blue 4GL dyeing at 100° C. for 60 minutes, and a light fastness of grade 5 after irradiation with a fetometer for 60 hours.

Example 5 Melamine 126 methanolic formalin (41,8
% concentration), 300 parts of methanol, and 1 part of concentrated hydrochloric acid were heated to boiling in a reactor equipped with a reflux condenser.

After dissolving the melamine, heating was continued for 40 minutes, and then the cooling water in the reflux condenser was drained, and 1 portion of water and 1 methanol were distilled off to obtain a transparent spinning solution E with a resin concentration of 60%.

The viscosity measured using a B-type rotational viscometer at 25°C was 1800 poise, and this solution was left in a constant temperature room at 25°C for 100 hours, but no devitrification or gelation was observed, and the viscosity and stringiness were also good. It's a powerful force of change.

Next, the spinning solution E is passed through a filter and put into a defoaming tank.
Under reduced pressure (20vurtHg) - After standing for day and night, temperature 40
It was extruded into water vapor at 200°C through a spinneret having 10 pores with a pore diameter of 0.25mm kept at 18°C to evaporate the methanol and harden the resin.
It was rolled up at a speed of n.

The spinning condition at that time was extremely good, and no yarn breakage was observed.

The resulting yarn was colorless, transparent, and glossy with a single yarn fineness of 5 denier.

Strength 3.4f/d, elongation 12%, knot strength 1.9g/d
, has an extremely excellent uniformity of 1.7%, and has an extremely high uniformity of 1 mm.
When wrapped around φ wire, it showed excellent flexibility.

The LOI value in the combustion test was 34.0, and
There was little smoke during combustion.

1. O using acid dye Alizarin Light Blue 4GL
The dye adsorption rate when dyed at 0°C for 60 minutes was 91%.
The light fastness after irradiation with a fetometer for 60 hours was grade 5.

Example 6 216 parts of trimethylolmelamine, 461 parts of ethanol, and 0.6 part of oxalic acid were put into a reactor, and the mixture was heated to 60 parts at reflux temperature.
After carrying out the etherification reaction, it was concentrated under reduced pressure and the resin concentration was 6.
A 0% clear spinning solution F was obtained.

The viscosity measured by a B-type rotational viscometer at 25°C was 1900 poise, and although this solution was left in a constant temperature room at 25°C for 100 hours, no devitrification gelation was observed, and the viscosity was 1900 poise.
It was no different than 0 poise.

Next, the spinning solution F is passed through a filter and put into a defoaming tank.
Under reduced pressure (2ommHg) - After standing for day and night, temperature 40'C
It was extruded into dry hot nitrogen at 250°C through a spinneret having 10 pores with a pore diameter of 0.25mz maintained at 200°C.
It was rolled up at a speed of 7 m 1 yr.

The spinning condition at that time was extremely good.

The single yarn fineness of the obtained yarn was 5 denier, and it was colorless, transparent, and glossy.

Strength is 3.5P/d, elongation 13%, knot strength 2, l'/
d.It has an extremely excellent uniformity of 1.7%, and ■m
It also showed excellent flexibility in the mφ wire eyelash test.

Furthermore, the LOI value of this yarn was 33.5, and little smoke was emitted during combustion.

When dyed using Alisarin Light Blue 4GL in the same manner as in Example 1, the dye adsorption rate was 91% and the light fastness was grade 5.

Comparative Example 1 126 parts of melamine, 648 parts of 39% formalin aqueous solution (
Formalin/melamine molar ratio 8/1) was prepared, and 20
The mixture was stirred and heated to 90° C. over several minutes to uniformly dissolve the mixture.

The mixture was then concentrated under reduced pressure at 60° C. for 2 hours to obtain a transparent spinning solution G with a resin concentration of 60%.

The viscosity measured using a B-type rotational viscometer at 25° C. was 1050 poise.

When a portion of this solution was left in a constant temperature room at 25° C. for 100 hours, a gelation phenomenon occurred and the solution solidified.

The concentrated solution G was passed through a filter into a degassing tank, left for one hour under reduced pressure (2 omvtHg), and then passed through a spinneret having 10 pores with a pore diameter of 0.25 mm maintained at a temperature of 30°C in dry nitrogen at 250°C. After extrusion, evaporation of water and curing of the melamine-formaldehyde resin initial condensate was performed, and winding was attempted at a speed of 200 m/ml, but winding was not possible, and winding was finally possible at a winding speed of 20 m/min. .

At that time, single thread breakage occurred many times.

The obtained yarn is a colorless and transparent yarn with a single yarn fineness of 6 denier, a strength of 2.2 f/d, an elongation of 5%, and a knot strength of 0.5 P/d.
, the degree of uniformity was 3.1%.

When this thread was wrapped around a 1 mm diameter needle, it broke, indicating poor flexibility.

As a result of a combustion test using an oxygen index combustion tester 0N-1 manufactured by Suga Test Instruments, the LOI value was 34.0, and little smoke was emitted during combustion (inflammability was demonstrated).

Using acidic dye Alizarin Light Blue 4GL, dye concentration 5% owf, ammonium acetate 3% owf, pH 3.5
When dyeing was carried out at 100'C for 60 minutes under the dyeing conditions of a bath ratio of 1:100, the dye adsorption rate was 90%.

The light fastness of this dyed thread after irradiation with a fetometer for 60 hours was grade 5.

Comparative Example 2 216 parts of trimethylolmelamine was stirred and dissolved in water at a temperature of 60°C for 1 hour, and the N-methylolmelamine concentration was 70%.
% solution H was prepared.

The viscosity at 25°C was 1900 poise.

When a portion of this solution was placed in a thermostatic chamber at 25° C., devitrification and gelation phenomena were observed after 10 hours, and solidification occurred after 100 hours.

The concentrated solution H was put into a degassing tank through a filter, left for one hour under reduced pressure (20 mmHg), and then heated with dry nitrogen at 250°C through a spinneret having 10 pores with a pore diameter of 0.25mm kept at a temperature of 25°C. Extruded into 15m/ml7
I wound it up at speed 2, but the single yarn broke frequently.

The obtained yarn has a single yarn fineness of 8 denier, is colorless and transparent, and has a strength of 23'? /d, elongation of 5%, knot strength of 0.6f/d, and uniformity of 3.6%.

When this thread was wrapped around a needle with a diameter of 1 mm, it broke, indicating poor flexibility.

The LOI value was 33.5, indicating excellent flame retardancy.

The dye adsorption rate was measured in the same manner as in Example 1 using the acid dye Alizarin Light Blue 4GL and found to be 89%.

The light fastness of this dyed yarn after irradiation with a fetometer for 60 hours was grade 5.

Example 7 Butyralization degree 65 in spinning solution A obtained in Example 1
After adding 5% polyvinyl butyral with a molecular weight of 1200 to solution A, it was put into a defoaming tank through a filter, left under reduced pressure (20 mmHg) for a day and night, and then heated to a temperature of 30
It was extruded into dry heated nitrogen at 280°C through a spinneret having 10 pores with a pore diameter of 0.25mm kept at 300°C.
It was rolled up at a speed of m/mm.

The spinning condition at that time was extremely good, and no single yarn breakage was observed per hour.

The obtained frayed yarn is a colorless and transparent yarn with a single yarn fineness of 5 denier, a strength of 3.9 g/d, an elongation of 14%, and a knot strength of 2.7?
/d, which was extremely excellent, and the yarn uniformity was 1.4%.

The combustion test results showed an LOI value of 32.5, and little smoke was emitted during combustion, indicating thermal infusibility.

That is, by adding polyvinyl butyral to the solution, improvement in spinnability (improvement in spinning speed) and improvement in yarn physical properties (strength and elongation, knot strength) were observed.

Example 8 After adding 5% of each of the following polymers to solution E obtained in Example 5, the polymers were passed through a filter and placed in a defoaming tank, and left under reduced pressure (20 mmHg) for a day and night.
Extruded into dry heated nitrogen at 280°C through a spinneret having 10 pores with a pore diameter of 0.25mm maintained at a temperature of 30°C.
It was rolled up at a speed of 350 m1m1n.

The results obtained are shown in Table 1. Example 9 216 parts of trimethylolmelamine, 461 parts of ethanol, 36 parts of polyethylene glycol with a molecular weight of 20,000,
After charging 0.6 part of oxalic acid into a reactor and carrying out an etherification reaction at reflux temperature for 60 minutes, the mixture was concentrated under reduced pressure to obtain a spinning solution with an ethanol-melamine initial condensate concentration of 60%.

This solution is passed through a filter and placed in a degassing tank under reduced pressure (
20mmHg) After standing for a day and night, it was extruded into dry heated nitrogen at 300°C through a spinneret having 10 pores with a pore diameter of 0.25mm kept at a temperature of 40°C, and 350 m1m1
It was rolled up at a speed of n.

The spinning condition at that time was extremely good.

The single yarn fineness of the obtained yarn was 5 denier, and it was colorless, transparent, and glossy.

Strength is 3.8g/d, elongation 14%, knot strength 2.6P/d
d. It has an extremely excellent uniformity of 1.4%, and the LO
The I value was 31.5, and little smoke was emitted during combustion.

Comparative Example 3 36 parts of polyvinyl alcohol with a degree of polymerization of 1700 and 216 parts of trimethylol melamine were heated and mixed and dissolved in 144 parts of water to prepare a spinning solution.

This solution was passed through a filter and put into a degassing tank, and under reduced pressure
After standing for a period of time, the temperature was kept at 40℃.The pore diameter was 0.25vtvt.
The fibers were extruded into dry heated nitrogen at 250° C. through a spinneret having 10 pores, and wound at a speed of 80 m/ml, but single fiber breakage occurred on average for 7 days in 1 hour.

The single yarn fineness of the obtained yarn was 5 denier, and it was colorless, transparent, and glossy.

Strength is 2.1P/d, elongation J4%, knot strength 1.2g/d
d, the degree of symmetry was 2.8%, which was inferior to that of the present invention.

The LOI value was 31.5, and little smoke was emitted during combustion.

Comparative Example 4 Ethylcellulose 3 having a 5% solution viscosity of 50 centipoise with an ethoxy group content of 49% was added to the spinning solution G obtained in Comparative Example 1.
A spinning solution was prepared by mixing an aqueous solution of ethyl cellulose prepared by dissolving 0 parts in 150 parts of water.

This solution is passed through a filter and placed in a degassing tank under reduced pressure (
After being left at 20 mmHg for 1 hour, the temperature was maintained at 30'C.

It was extruded into dry heated nitrogen at 250° C. through a spinneret having 10 pores with a pore diameter of 0.25 mm and wound at 50 m/mi.

The single yarn breakage per hour was 5 days, and the obtained yarn was a colorless and transparent yarn with a single yarn fineness of 6 denier and a strength of 2. ]7/
d, elongation 14%, knot strength 0.9f/d, symmetry 2.7
%Met.

As a result of the combustion test, the LOI value was 315.

Example 11 After adding various curing agents to the spinning solution obtained in Example 1.7, it was passed through a filter and placed in a degassing tank under reduced pressure (20 m
mHg) After standing for a day and night, the pore size was kept at 30°C.
The second
It was extruded into dry hot nitrogen at each atmospheric temperature shown in the table and wound at each spinning speed.

The results obtained are shown in Table 2.

Comparative Example 5 Aqueous solution 4 containing formaldehyde 90y (3.0 mol)
After adding 54 g of polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 99.9% to 20 g and heating and dissolving at a temperature of 95°C, melamine 126f (1.0 mol) was added and the mixture was stirred for 5
The reaction was carried out at 0°C for 1.5 hours.

The aqueous solution after the reaction is polyvinyl alcohol modified melamine.
The concentration of formaldehyde initial condensate was 42.5% by weight.

When this aqueous solution was kept at 30°C, it began to turn into a devitrified gel in 4 hours, and a decrease in stringability was observed.

This solution is passed through a filter and placed in a degassing tank under reduced pressure (
After standing for 1 hour (20 mmHg), the material was extruded into dry heated nitrogen at 290°C through a spinneret having 10 pores with a pore diameter of 0.25 mm kept at a temperature of 30°C, and 260ml/ml/n
When winding at a speed of
It decreased to n.

The obtained yarn was colorless and transparent with a single yarn fineness of 4 denier, a strength of 2.5 f/d, and an elongation of 10%, which was inferior to that of the present invention.

Example 12 The fiber obtained in Example 1 was cut into 51 mm pieces, and then heat treated in heated air at a temperature of 180° C. for 30 minutes to further advance curing.

The strength of the obtained fiber is 4.2'i? /d, elongation is 11%
The LOI value was also excellent at 35.0.

Example 13 After cutting the fiber obtained in Example 9 into 44 mm, the fiber was heated to a temperature of 1.
Curing was further progressed by heat treatment for 30 minutes in heated nitrogen at 80°C.

The strength of the obtained fibers was 4-. 5P/d and elongation were improved by 13%, and the LOI value was also excellent at 33.0.

Example 14 The fiber obtained in Example 5 was heated by guiding it to a heating roller (diameter 100 mm) at a temperature of 180°C and winding it 8 times, and then heated it with a stretching roller at a stretching rate of 0% (heating After the film was taken up under tension by setting the linear speed of rotation of the roller and the drawing roller to be equal, it was rolled up at a speed of 300ml/min.

The obtained fiber had a strength of 3.5 P/d and an elongation of 12%.

Example 15 In Example 14, the linear speed of rotation of the heating roller and the stretching roller was changed so that the film was drawn at a stretching ratio of 50% and then rolled up at a speed of 450 ml/mm.

The strength of the obtained fiber is 4.2? /d, elongation was 7%, and the LOI value was 34.5.

Example 16 After adding 1% by weight of acetamide to the spinning solution obtained in Example 4, it was passed through a filter and placed in a defoaming tank, and after being left under reduced pressure (20 mmHg) for a day and night, the pore diameter was 0 while maintaining the temperature at 40'C. It was extruded into dry heated nitrogen at 200° C. through a spinneret having 12 pores of .2 Q mm and wound up at a speed of 200 m/m.

The fibers are heated at a heating temperature of 150°C and heated by a heating roller with a diameter of 100mmφ, and then heated by a stretching roller to 150%
After stretching, the film was put into a heating box at a temperature of 230°C, heat-treated for 1 minute, and then rolled up at a winding speed of 300 m x 1 m1.

This fiber is a colorless and transparent glossy crimped yarn with a single yarn fineness of 4 denier, a strength of 4.9 f/d, an elongation of 13%,
The uniformity was 1.2%, which was extremely excellent.

Further, this yarn showed an LOI value of 350, a dyeing rate of 91% when dyed with Alizarin Light Blue 4GL at 100° C. for 60 minutes, and a light fastness of 5th grade after 60 hours of irradiation with a fetometer.

Claims (1)

[Scope of Claims] 1. In the presence of alcohol, a small amount (20% in total) of the alkylol groups of the melamine-aldehyde initial condensate is etherified, and the resulting alcohol-modified melamine-aldehyde resin initial condensate solution is treated with fiber-forming properties. A method for producing alcohol-modified melamine resin fibers, which comprises spinning in an atmosphere. 2. In claim 1, the alcohol-soluble polymer is added in an amount of 30% by weight based on the initial condensate of alcohol-modified melamine-aldehyde resin. 3. A method for producing alcohol-modified melamine resin fibers, characterized in that the spinning solution contains an acidic substance or a thermally decomposed substance in the spinning solution. One or more substances that can generate acidic substances, 0.5 to 5.0 to the entire composition
A method for producing alcohol-modified melamine resin fibers, characterized by using a spinning solution containing % by weight. 4. A method for producing an alcohol-modified melamine resin fiber according to claim 1, 2 or 3, characterized in that the melamine-aldehyde initial condensate is a melamine-formaldehyde initial condensate. 5. Claims 1, 2, or 3 are characterized in that the alcohol as the etherifying agent for an alkylol group is a primary aliphatic alcohol or a secondary aliphatic alcohol having 5 or less carbon atoms. A method for producing alcohol-modified melamine resin fiber. 6. In claim 2 or 3, an alcohol-modified melamine resin system characterized in that the alcohol-soluble polymer is at least one selected from the group consisting of polyvinyl acetate, polyvinyl acetal, and polyvinyl butyral. Method for producing fibers. 7. The alcohol-modified melamine according to claim 2 or 3, wherein the alcohol-soluble polymer is at least one selected from the group consisting of cellulose nitrate, methyl cellulose, and ethyl cellulose. A method for producing a resin fiber. 8. A method for producing an alcohol-modified melamine resin fiber as set forth in claim 2 or 3, characterized in that the alcohol-soluble polymer is polyethylene glycol. 9. In claim 3, the method for producing an alcohol-modified melamine resin fiber, characterized in that the acidic substance is an organic acid.10 In claim 3, the substance that can be thermally decomposed to produce an acidic substance is an inorganic acid. A method for producing an alcohol-modified melamine resin fiber, characterized in that the fiber is an ammonium salt. 11. In claim 3, the substance that generates an acidic substance upon thermal decomposition is an ammonium salt of an organic acid. 12. A method for producing an alcohol-modified melamine resin fiber, characterized in that the substance that can be thermally decomposed to produce an acidic substance is a formic acid ester. Manufacturing method. 13. A method for manufacturing an alcohol-modified melamine resin fiber as set forth in claim 3, characterized in that the substance that can be thermally decomposed to produce an acidic substance is an acid amide. 14. Claim 1 15. A method for producing an alcohol-modified melamine resin fiber, characterized in that at least 30% or more of the alkylol groups are etherified. A method for producing alcohol-modified melamine resin fibers, characterized in that the fiber-forming atmosphere is heated gas at 70°C or higher.16 Claim 15, wherein the fiber-forming atmosphere is heated at 150 to 330°C. A method for producing an alcohol-modified melamine resin fiber, characterized in that the heated gas is a gas. 17. In claim 15 or 16, the heated gas is an inert gas, air or water vapor. A method for producing alcohol-modified melamine resin fibers. 18. In the presence of alcohol, at least 20% of the alkylol groups of the melamine-aldehyde pre-condensate are etherified, and the resulting alcohol-modified melamine-aldehyde resin pre-condensate solution is obtained. A method for producing alcohol-modified melamine resin fibers, which comprises spinning the fibers into a fiber-forming atmosphere and then heat-treating the fibers at a temperature of 70 to 300°C. 19 Claim 18 provides an alcohol-modified melamine resin based fiber characterized by using a spinning solution containing 30% by weight or less of an alcohol-soluble polymer based on the alcohol-modified melamine-aldehyde resin initial condensate. Production method. 20 In claim 18 or 19, the spinning solution contains one or more acidic substances or substances that can be thermally decomposed to produce acidic substances in an amount of 0.5 to 0.5 to 100% of the total composition.
A method for producing alcohol-modified melamine resin fibers, characterized by using a spinning solution containing 5.0% by weight. 21. The method for producing alcohol-modified melamine resin fibers according to claim 18, characterized in that the spun fibers are heat-treated at a temperature of 100°C to 250°C. 22. The method for producing alcohol-modified melamine resin fibers according to claim 18, which comprises heat-treating the spun fibers at a temperature of 100°C to 250°C without tension. 2. A method for producing alcohol-modified melamine resin fibers according to claim 18, which comprises heat-treating the spun fibers under tension at a temperature of 100°C to 250°C. 24. The method for producing alcohol-modified melamine resin fibers according to claim 18, characterized in that the spun fibers are dry-heat stretched by 10% or more at a temperature of 100°C to 250°C.