JPS61225371A - Fiber processability enhancer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fiber processability improver. Generally, fibers are subjected to various processes such as scouring, bleaching, dyeing, saw pinking, etc. in order to increase their commercial value before becoming final fiber products. These treatments are performed using various chemicals, dyes, etc., but they can also be caused by impurities contained in the fiber itself, impurities attached during previous processes, or hardness components contained in the water used. Problems arise such as poor penetration of chemicals, resulting in non-uniformity, or rough texture. The present invention provides an agent for smoothly and favorably processing fibers as described above, that is, a processability improver. Generally, this is carried out using an alkaline agent, a surfactant, or a solvent, and among these methods, a method using a combination of an alkaline agent and a surfactant is widely used. Scouring of cellulose fibers removes water-repellent substances such as primary impurities (natural impurities) such as fats and waxes contained in the fibers and secondary impurities (additional impurities) such as machine oil, thereby increasing the wettability and water absorption of the fibers. imparting sex, followed by bleaching,
It is carried out as a preparatory step in dyeing, saw pinking, finishing, and other processes to ensure uniform permeation of chemicals, ease of operation, and increase the value of the product, as well as to bring out the characteristics of the fiber. However, the above-mentioned scouring method using a combination of an alkaline agent and a surfactant has the following problems, and a solution to these problems has been desired.

In other words, when the water used during scouring has high hardness, oil and fat components are hydrolyzed by an alkaline agent, and the fatty acids produced at this time combine with the hardness components of the water to form so-called metal soaps, which make the scouring operation difficult. deposited on the receiving fibers.

Since this metal soap cannot be easily emulsified or dispersed with the usual surfactants used in scouring, it remains on the fibers even after the scouring process, and develops water repellency, which improves the required wettability of the fibers. Bleaching following scouring with loss of water absorption,
This results in poor penetration of chemicals during processes such as dyeing, soaping, and finishing, leading to problems.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted intensive research and found that polyacrylates were effective and had already proposed them (Japanese Patent Application Laid-Open No. 187669/1983). However, as a result of further research, the polymer of the present invention was found to be effective. It has been found that this method has even better effects.

Generally, silk consists of fibroin and sericin surrounding it, but it is necessary to remove sericin in order to produce the original properties of silk. To solve this problem, scouring (so-called silk polishing) is carried out using a surfactant and an alkaline agent, but the following problems have been desired to be solved.

That is, if the water used during silk kneading has high hardness,
For example, if soap or the like is used as a surfactant, it will combine with the hardness components of the water to produce water-insoluble metal soap, which will adhere to silk fibers, or if sodium silicate or the like is used as an alkaline agent, water will This combines with the hardness components of the silk fibers to form water-insoluble silicate, which adheres to the silk fibers to give them a rough and hard texture. This will lead to poor penetration and cause problems. Also, if you use too much soap, it will take a long time to knead the silk, which may cause damage to the silk.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted intensive research, found that polyacrylates were effective, and have already proposed (Japanese Patent Application No. 7859/1982)
However, as a result of further research, it was discovered that the polymer of the present invention has even more excellent effects.

In addition, recycled fibers such as rayon and cupola, semi-synthetic fibers such as diacetate and triacetate, polyester,
Textiles made of synthetic fibers such as nylon and acrylic do not contain the primary impurities found in natural cellulose fibers, but they are used to make spinning oil, twisting, and weaving easier. Contains secondary impurities such as glue, oil, and dirt. These impurities cause the texture to be rough and hard, impede the permeability of dye liquids and resin liquids during dyeing and finishing processes, and cause uneven dyeing and uneven resin adhesion. must be removed. Thickening agents include natural starch agents such as potato starch and wheat starch, and synthetic thickening agents such as polyvinyl alcohol and vinyl copolymer.

Starch-based natural sizing agents generally have incomplete adhesion and have poor adhesive properties, so synthetic sizing agents, especially acrylic acid polymers, are widely used. To remove impurities such as spinning oils, glues, oils, and dirt, scouring using a surfactant and an alkaline agent such as caustic soda is generally performed, but the following problems arise: A solution to this problem was desired.

That is, when the water used during scouring has high hardness, for example, the oil and fat components in the oil agent are hydrolyzed by an alkaline agent, and the fatty acids produced at this time combine with the hardness components of the water to form so-called water-insoluble substances. Metallic soaps are formed and redeposited onto the fibers undergoing the scouring operation. This metal soap cannot be easily emulsified or dispersed with the usual surfactants used in scouring, so it remains on the fibers even after the scouring process, causing rough texture and coloring after scouring. This can lead to poor penetration of chemicals during finishing processes and other processes, causing problems. Alternatively, synthetic sizing agents such as acrylic acid polymers combine with the hardness component of water and re-deposit on fibers undergoing scouring operations as water-insoluble glues, causing similar problems. It turns out.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. were used in combination, but the effects were not sufficient. Therefore, the present inventors conducted intensive research and found that polyacrylate is effective. However, as a result of further research, it was discovered that the polymer of the present invention has even more excellent effects.

Next, it is known that polyester fibers undergo hydrolysis in a mature alkaline solution and exhibit a unique phenomenon in which the surface layer of the fibers gradually dissolves and becomes thinner. When this treatment is applied to woven or knitted fabrics, the fiber gaps increase, making the woven or knitted fabric bulky, and the contact pressure between yarns decreases, resulting in a soft, so-called silky texture. Therefore, this alkali treatment is often used for polyester fibers as a treatment before the dyeing process, but the following problems arise and a solution has been desired.

That is, when the water used for alkali weight loss is high in hardness, the polyester oligomer, which is a product of alkali weight loss, combines with the hardness component of the water and becomes a water-insoluble salt.
This adheres to the fibers and causes them to have a rough and hard texture, resulting in poor penetration of chemicals during subsequent dyeing, finishing, and other processes, causing problems. Alternatively, the same applies to washing steps before and after alkali reduction and neutralization.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted intensive research and found that polyacrylates were effective and had already proposed them (Japanese Patent Application No. 59-7859). However, as a result of further research, the polymer of the present invention was found to be effective. We have found that it has an even better effect. Generally, cellulose fibers still contain natural pigments even after scouring, so this natural pigment and even secondary attached colored substances can be removed. Bleaching is done for this purpose. Bleaching methods include peroxide bleaching, chlorine bleaching, and sodium chlorite bleaching, but peroxide bleaching does not damage the fibers, is easy to operate, and provides durable whiteness. , generally widely used. This peroxide bleaching is achieved by oxidatively decomposing the pigments in the cellulose fibers using nascent oxygen generated by the decomposition of hydrogen peroxide, but this oxidative decomposition is more efficient when carried out on the alkaline side. Since it is highly effective, an alkaline agent such as caustic soda is used in combination, and sodium silicate is also used as a stabilizer for hydrogen peroxide decomposition under alkaline conditions. Therefore, the bleach bath composition includes hydrogen peroxide,
It will be composed of alkali (such as caustic soda) and sodium silicate (such as those with a molar ratio of Sin: Na, O = 2.5: 1), but if the water used for bleaching has a high hardness In this case, sodium silicate combines with the hardness components of water to produce water-insoluble silicates such as calcium silicate and magnesium silicate, which deposit on the fibers and do not improve the whitening of the fabric and deteriorate the texture. However, there is a problem in that the material hardens roughly and also increases the coefficient of friction with the sewing machine needle, impeding sewing performance, and a solution to this problem has been desired.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted intensive research, found that polyacrylates were effective, and have already proposed (Japanese Patent Application Laid-Open No. 59-211675
However, as a result of further research, it was discovered that the polymer of the present invention has even more excellent effects.

Generally, cellulose fibers are dyed using dyes such as direct dyes, sulfur dyes, threne dyes, naphthol dyes, reactive dyes, basic dyes, and acid dyes. Among these, direct dyes are dyed by physicochemical adsorption and the color fastness can be easily improved by post-dyeing fix treatment, while sulfur dyes have excellent color fastness but low color clarity. Thren dyes have extremely good color fastness, and naphthol dyes have relatively clear color tones and good color fastness, but they require complicated processes such as dipping the fibers with a primer and developing the color through diazotization treatment with a color developer. Reactive dyes dye by forming a covalent bond between the dye and the fiber, resulting in a clear color tone and excellent color fastness.Basic dyes require a complicated mordant process and are dyed with high dye fastness. Each type of dye has its own characteristics, such as low strength, complicated dyeing methods, and unstable hues for acid dyes. Therefore, among these dyes, direct dyes, threne dyes, reactive dyes, etc. are the main dyes. Although there are some problems with direct dyes, metal-containing azo type dyes account for a large proportion, and such metal-containing dyes are also used in many acid dyes and reactive dyes. Metal-containing dyes include chromium,
Dyeing with dye molecules is a coordination bond between a metal atom such as copper, cobalt, iron, or aluminum, and a dye molecule. Conventionally, dyeing with this type of dye has had the following problems, and solutions to these problems have been desired. That is, when the hardness of the water used during dyeing is high, the hardness component of the water inhibits the solubilization and dispersibility of the dye, resulting in a problem in that uniform dyeing cannot be obtained.

To improve this, chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxylethylenediaminetriacetic acid, and nitrilotriacetin quacinde are sometimes used together, but in this case, the chelating agent is Although it has some effect on uniform dyeing by collecting some of the hardness components, the effect is small, and what is worse is that the chelating agent has a strong effect of forming a complex salt with the metal as the coloring group in the dye. As a result, the dye-metal coordination bond becomes unbalanced, resulting in a fatal problem in that the hue of the dyed cloth deviates from the hue that would be obtained from the dye used. Furthermore, threne dyes, which play an important role in the dyeing of cellulosic fibers, are water-insoluble dyes containing two or more carbonyl groups, and are reduced with alkali to convert the carbonyl groups into sodium leuco salts. Since this is water-soluble and has a high affinity with cellulose fibers, it is dyed in this state, and then the sodium leuco salt is oxidized to a quinone form using an acid to develop color, and at the same time it becomes water-insoluble again. However, this dyeing also has the following problems, and a solution to these problems has been desired. In other words, when the water used during dyeing has high hardness, the hard components of the water combine with the dye to form a dye dimer, which is insoluble in water and has no affinity with cellulose fibers. There was a problem in that the color density that should have been obtained from the dye density used could not be obtained.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted extensive research and found that polyacrylates were effective and had already proposed them (Japanese Patent Application Laid-Open No. 59-211688). However, as a result of further research, the polymer of the present invention was found to be effective. It has been found that this method has even better effects.

In general, natural fibers such as silk and wool, recycled fibers such as rayon and cupola, semi-synthetic fibers such as diacetate and triacetate, and synthetic fibers such as polyester, nylon and acrylic, have a higher commercial value as final fiber products. , dyeing is also done to add fashionability.

There are various methods for this dyeing, but for example, in the batch dyeing method, the object to be dyed, such as fiber, thread, woven fabric, knitted fabric, nonwoven fabric, or textile product, is immersed in a dye bath in which the dye is dissolved. A method is used in which the dye is adsorbed onto the object to be dyed through the effects of temperature and time. In order to obtain uniform dyeing properties, dyeing aids are used in the dye bath according to each fiber and dye, but depending on the dyeing conditions, or if the water used is too hard. Even if a leveling agent with excellent dye dispersibility is used, or even if a dispersant is used in addition to the dye dispersant already contained in the dye, the dye may aggregate or precipitate in the dye bath. As a result, uneven dyeing such as tarring and uneven dyeing may occur. In addition, in order to improve the fastness of various dyes by removing unfixed and undyed dyes remaining on the fiber surface due to dyeing, reduction washing is performed.
However, even if dyeing is done using dyeing aids such as leveling agents and dispersants, unfixed and undyed dyes often remain on the fiber surface.
In many cases, reduction cleaning properties are extremely poor.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted intensive research and found that polyacrylate was effective, and have already proposed it (Japanese Patent Application No. 12710/1982).
However, as a result of further research, it was discovered that the polymer of the present invention has even more excellent effects.

In addition, in continuous dyeing methods such as thermosol dyeing and bud-steam dyeing, the material to be dyed, such as woven, knitted, or nonwoven fabrics, is padded in a dye solution and then colored by dry heat or steaming. A dyeing method is used. In order to obtain uniform dyeing properties and increase the dye utilization rate, dispersants and thickening agents are used in combination with each fiber material and dye in the dye bath. Depending on the conditions, or if the water used is highly hard, even if a dispersant or sizing agent is used in combination, the dye may aggregate, precipitate, or migrate, resulting in uneven dyeing and other defects. There are cases where uniform dyeing occurs. Furthermore, depending on the type of glue, it may combine with the hardness components of water and turn into an insoluble glue, resulting in insufficient desizing properties during subsequent washing (de-sizing) associated with dyeing. Alternatively, similar problems arise in various textile printing and dyeing methods that use sizing agents such as direct printing, colored anti-discharge printing, and white anti-discharge printing, such as uneven dyeing and de-sizing during washing (de-sizing) associated with dyeing. Problems such as decreased sexuality may occur.

In order to improve this problem, ethylenediaminetetraacetic acid, sodium tripolyphosphate, etc. have been used in combination, but their effects were not sufficient. Therefore, the present inventors conducted intensive research and found that polyacrylate was effective, and have already proposed it (Japanese Patent Application No. 12710/1982).
However, as a result of further research, it was discovered that the polymer of the present invention has even more excellent effects.

Generally, reactive dyes and/or direct dyes are used for cellulosic fibers, while disperse dyes,
It is dyed using acid dyes, basic dyes, etc. For dyed products, unfixed dyes are removed, and for printed products, the paste is removed to make the color pattern clearer and the texture better. A soaping process is generally used to improve the fastness of the product. In the soaping process, in the case of dyed products using only disperse dyes, reduction washing is performed to improve various fastness properties.

However, when using reactive dyes and/or direct dyes, unfixed dyes that have fallen off during soaping tend to re-adhere to the fibers, reducing the clarity of the dyed product.Especially in printed materials. If contamination of hot water occurs, the quality of the dyed product will be significantly lowered.

Therefore, in order to prevent this contamination and to improve various fastness properties, it is common practice to add a surfactant, generally called a soap pink agent, to the soaping bath before soaping. There is.

Conventionally, as these soap pink agents, ethylene oxide adducts of aliphatic amines, ethylene oxide adducts of nonylphenol, ethylene oxide adducts of fatty acids, fatty acid soaps, higher alcohol sulfates, etc. have been used. Furthermore, polyacrylates and the like have recently been used.

However, even with the use of these saw pink agents, stain prevention and fastness improvement are still insufficient, and improvements have been strongly desired in the dyeing industry. As a result of intensive research aimed at solving the above-mentioned problems associated with fiber processing, they discovered that processability could be improved by using a specific compound, and completed the present invention.

That is, the present invention relates to the following general formula: where Y is one or more comonomers, n is on average at least 4, p is from 0 to about 2, and q
is at least 1), R1 and R2 are each any chemically stable group that stabilizes the copolymer against rapid depolymerization in alkaline solutions, and M is an alkali metal, Ammonium, an alkyl group having from 1 to about 4 carbon atoms, and an alkanolamine group having from 1 to about 4 carbon atoms in the alkyl chain). The purpose is to provide an agent for

Generally, the polymers of the present invention are prepared by mixing an ester of glyoxylic acid, optionally one or more substances capable of polymerizing with said ester of glyoxylic acid, and a polymerization initiator under polymerization conditions; (B) can be prepared by stabilizing the resulting copolymer against rapid depolymerization in alkaline solutions. The stabilized copolymer can be saponified to form the copolymer salt.

Any ester of glyoxylic acid can be used as a starting material to make the polymers of this invention. Such esters can be prepared by reacting alcohols containing from 1 to 4 carbon atoms with glyoxylic acid hydrochloride under conditions known to those skilled in the art. Suitable esters include, for example, those having from 1 to about 4 carbon atoms in the ester, such as methyl, ethyl, propyl, isopropyl, butyl, inbutyl, and the like. Other esters of glyoxylic acid also interfered with the polymerization) or the conversion of the hemiacetal ester of glyoxylic acid to the corresponding aldehyde ester, or the alkali metal salts of the esters stabilized. It can be used as long as it does not interfere with saponification.
Esters of such glyoxylates are also equivalent for the purposes of this invention. Methyl and ethyl esters are preferred.The resulting hemiacetal ester of glyoxylic acid can then be prepared by any method known to those skilled in the art, for example by the following general formula (wherein E is an alkyl group having 1 to 4 carbon atoms). can be converted into the corresponding aldehyde ester by reacting the ester represented by the above formula with phosphorus pentoxide. The resulting aldehyde ester is then polymerized using a suitable initiator.

If desired, any comonomer known to those skilled in the art can be polymerized with the aldehyde ester to form the polymers of the present invention. All that is required is that the comonomer has at least two reactive sites and that the polymers of the present invention are not depolymerized in alkaline solution or that would interfere with polymerization. Suitable comonomers include, for example, epoxy compounds such as ethylene oxide, propylene oxide, epihalohydrin epoxysuccinate, etc., aldehydes such as formaldehyde, acetaldehyde, etc., and aldehydes containing up to 20 carbon atoms. It is particularly advantageous if the comonomers contain carmexyl groups as substituents. Preference is given to comonomers having 1 to 4 carbon atoms, such as ethylene oxide, formaldehyde or acetaldehyde.

Mixtures of copolymers can be polymerized with the aldehyde esters to form terpolymers, or more complex polymer structures can be formed. For example, a mixture of the same comonomer groups, such as a mixture of epoxy compounds such as ethylene oxide and propylene oxide, can be polymerized with an aldehyde ester to form a terpolymer. Even if a copolymer may inhibit polymerization when used alone, it can be improved by mixing it with a low molecular weight aldehyde such as formaldehyde or acetaldehyde and polymerizing it with an aldehyde ester. Terpolymers can be formed that are randomly distributed along the polymer chain. Numerous other examples exist and will be apparent to those skilled in the art in light of this specification.

A mixture of ethylene oxide and formaldehyde is one example. Any initiator can be used in this polymerization; nonionic or ionic initiators give satisfactory results. Suitable initiators include, for example, amines such as triethylamine, 2-hydroxypyridine-H20 complex, strong Lewis acids such as boron trifluoride or boron trifluoride diethyl etherate, phosphorous pentafluoride, stannous chloride, etc. Can be mentioned. Trace amounts of hydroxy or cyanide ions also trigger polymerization. Good effects can also be obtained using sodio derivatives such as diethyl sodiomalonate or sodiomethylmalonate ester.

The number of carboxylate groups in the polymers of this invention is important. This is because the number of carboxylate groups affects the usefulness of the corresponding polymer salt as a chelating agent, sequestering agent, and detergent builder. Therefore, the nature of the comonomer (i.e., the nature of Y), the molar ratio of comonomer to aldehyde ester (i.e., the values of p and q), and the number of repeating units in the polymers of the invention (i.e., the n average values) are interrelated and important.

This is because they affect the number of carboxylate groups in the polymer.

As mentioned above, aldehyde esters can be polymerized with any comonomer or mixture of comonomers;
It will be apparent to those skilled in the art that the carboxylate groups may be dispersed broadly along the polymer chain or that large comonomers that inhibit chelate formation of the dicarboxylate groups ( (or comonomer mixtures) reduce the effectiveness of the corresponding polymer salts as sequestering agents, chelating agents, and builders. The drop in this effect is
There may be some offset if the comonomer or one of the comonomers contains a carboxylate group. It is preferred to use relatively small comonomers, such as ethylene oxide or formaldehyde, which do not inhibit cychelate formation by steric hindrance in which the carboxylate groups are broadly dispersed.

The molar ratio of aldehyde ester to comonomer (or comonomers) (ie, the q:p value) is important. Although there is no theoretical upper limit on the number of moles of comonomer (or comonomers) relative to the number of moles of acetal carboxylate moiety in the polymer, the ratio of comonomer to acetal carboxylate moiety When the molar ratio exceeds about 2:1 (ie, p is less than about 2 and q is 1), the polymer salt loses much of its effectiveness as a fiber processability enhancer of the present invention. It is preferred that the molar ratio of acetal carboxylate to comonomer is about 1:1 (i.e., p and q are each about 1), but higher, for example 5:
1 or even 99:1 (ie p is 1 and 4 is at least about 99) are also preferred. Of course, the polymers of the invention are highly effective in the absence of comonomers, ie when p is equal to zero.

Preferably, the polymers of the present invention have an average number n of repeating units from about 10 to about 200, and even more preferably from about 50 to about 100 repeating units in the chain.

Other important factors that are thought to control the chain length of the polymer are (I) the type and purity of the initiator, (2) the polymerization temperature, (5) the purity of the starting material, and (4) the presence of a catalyst. The extent of this is mentioned. As will be apparent to those skilled in the art, all of these factors are interrelated and the desired chain length can be easily controlled by simple experimentation adjusting these variables. After polymerizing the aldehyde ester with or without comonomer, any chemically reactive group can be attached to the end of the polymer, in which case trifluor Preferably, ionic catalysts such as boron etherate, trifluoroacetic acid, sulfuric acid, potassium carbonate, etc. are used. All that is required is that the chemically reactive groups mentioned above stabilize the polymer against rapid depolymerization in alkaline solutions. For example, suitable chemically stable end groups include stable substituents derived from otherwise stable compounds. Such compounds include, for example, alkanes such as methane,
Ethane, propane, butane and higher alkanes such as decane, dodecane, octadecane, alkenes such as ethylene, propylene, butylene, decene, dodecene, etc., branched hydrocarbons (both saturated and unsaturated) such as 2-methylbutane, 2-methylbutene, 4-butyl-2,3-dimethyloctane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., cycloalkanes such as cyclohexane and cyclohexene, haloalkanes such as chloromethane, chlorobutane, dichloropentane, etc. , alcohols such as methanol, ethanol, 2-glopanol, cyclohexanol, sodium phenate, etc., and polyhydric alcohols such as C1.
2-ethanediol, 1,4-benzenediol, etc.
Mercaptans such as methanethiol, 1,2-ethanedithiolnato, ethers such as methoxyethane methyl ether, ethyl ether, ethoxypropane and cyclic ethers such as ethylene oxide, shrimp chlorohydrin, tetramethylene oxide, etc., and carboxy Rate-containing compounds include, for example, alkali metal salts of carboxylic acids, esters of carboxylic acids, anhydrides, and the like.

Particularly suitable terminal groups include alkyl groups, oxygen-containing alkyl groups and oxygen-containing cyclic alkyl groups such as oxyalkyl groups such as methoxy, ethoxy, etc., carboxylic acids such as aldehydes, ethers and other oxygen-containing alkyl groups such as 10OHCH, QC! 2H,, (-QC! is an alkyl group, and R is hydrogen or 1-8
is an alkyl group having 5 carbon atoms. As will be apparent to those skilled in the art in view of this specification, the chemically stable end groups at the polymer ends may be the same or different.

When the fiber processability improver of the present invention is used in the processing of fibers, good results can be obtained not only in the processing but also in subsequent processing.

By scouring cellulose fibers in the coexistence of an alkali agent, a surfactant, and the fiber processability improver according to the present invention, superior wetting of the fibers after the scouring process is achieved compared to conventional scouring methods. It can give properties and water absorption properties,
In subsequent steps such as bleaching, dyeing, and finishing, the penetration of chemicals is uniform and good, making operations easier. Although the mechanism by which the problem of poor scouring is solved by coexisting a fiber processability improver made of the polymer of the present invention with an alkaline agent and a surfactant during scouring of cellulose fibers is not necessarily clear, This is thought to be due to the extremely excellent metal ion sequestration ability and dispersion power possessed by the polymer.

Conventional methods can be used for scouring, such as pad-steam method, pressure boiling method, boiling method, and heating from about 60℃ to 100℃.
The immersion method up to ℃ or other methods can be applied. Furthermore, when the processability improver of the present invention is actually used, in order to streamline the process, scouring may be carried out simultaneously with the desizing process, which is a pre-process of the scouring process, or the bleaching process, which follows the scouring process, within a range that does not impede scouring properties. It can also be applied to

The amount of the fiber processability improver of the present invention varies depending on the amount of the scouring agent, etc., but is generally 0.01 to 20 t in the scouring bath.
(solid content conversion)/! , preferably 0.04 to 10 f (in terms of solid content)/i.

If the treatments performed before the dyeing process, such as scouring, scouring of various grain fibers, and alkaline reduction of polyester fibers, are carried out in the presence of the fiber processability improver according to the present invention, they are superior to conventional methods. A good treatment effect can be obtained and a good texture can be imparted, and at the same time, in the subsequent steps such as dyeing and finishing, the penetration of chemicals is uniform and good, and operations can be performed easily. The mechanism by which the above-mentioned problems are resolved when a fiber processability improver consisting of the polymer of the present invention is present during treatments such as scouring, scouring of various fibers, and alkaline reduction of polyester fibers is not necessarily clear. However, this is thought to be due to the excellent metal ion sequestering ability and dispersion power of the polymer according to the present invention.

By bleaching cellulose fibers in the coexistence of hydrogen peroxide, alkali, sodium silicate, and the fiber processability improver of the present invention, superior white discoloration, texture, and texture can be achieved compared to conventional bleaching methods. Can provide sewing properties. Although the mechanism by which the problem of poor bleaching is resolved by coexisting the fiber processability improver made of the polymer of the present invention with hydrogen peroxide, alkali, and sodium silicate during bleaching of cellulose fibers is not necessarily clear, This is believed to be due to the extremely excellent metal ion sequestration ability and dispersion power of the salt of the polymer of the present invention.

The amount of the fiber processability improver of the present invention varies depending on the amount of bleach, etc., but is generally 0.01 to 20 f in the bleach bath.
(solid content conversion)/! , preferably 0.04 to 10 t (solid content equivalent)/! used.

When cellulose fibers are dyed with metal-containing dyes or thren dyes using highly hard water, these dyes and the fiber processability improver of the present invention can be used in combination with the conventional dyeing methods. In comparison, excellent staining properties can be obtained.

Although the mechanism by which dyeing problems are solved by the coexistence of a fiber processability improver made of the polymer of the present invention during dyeing of cellulose fibers with metal-containing dyes is not necessarily clear, it is clear that the processability improver has extremely excellent properties. The metal ion sequestration ability and dispersion power act only on the hardness component of water and do not act on the metal as a color forming group in the dye, so the balance of the dye-metal coordination bond is not disrupted and uniform dyeing can be obtained. At the same time, it is thought that this is because the hue of the dyed cloth does not shift. Furthermore, the mechanism by which the dyeing problem is solved by coexisting the fiber processability improver made of the polymer of the present invention during dyeing of cellulose fibers with thren dyes is not necessarily clear, but it is known that the fiber processability improver has This is thought to be due to the extremely excellent metal ion sequestration ability and dispersion power. The amount of the fiber processability improver of the present invention varies depending on the type and concentration of the dye used, but is generally 0.01 to 20 t (solid content equivalent) per dye bath. ,
Preferably 0.04-10f (solid content equivalent)/! Added.

The fiber processability improver of the present invention also exhibits excellent effects for dyeing fibers other than cellulose fibers.

By improving the fiber processability of dyeing such as dip dyeing, continuous dyeing, and printing using the present invention in the coexistence of dyes, various problems as mentioned above can be solved, and tarring and uneven dyeing can be eliminated, resulting in good results. The polymer according to the present invention has dyeability, and also facilitates the processing itself and improves processing performance in reduction washing and de-sizing washing accompanying dyeing, although the mechanism is not necessarily clear. This is believed to be due to the excellent metal ion sequestering ability and dispersion power.The amount of the fiber processability improver of the present invention added is the same as in the case of dyeing cellulose fibers.

In addition, even if other chemicals such as softeners, scouring agents, and penetrants are used in the dye bath during dyeing, they may be used as long as they do not inhibit the effects of the fiber processability improver of the present invention. The fibers to which the fiber processability improver of the present invention can be used are not particularly limited, and include natural fibers such as cellulose fibers, wool, and silk, as well as various synthetic fibers. Applicable to cellulose fibers such as cotton and hemp, recycled fibers such as rayon and cupola, semi-synthetic fibers such as diacetate and triacetate, synthetic fibers such as nylon, polyester, and acrylic, and/or mixtures of these fibers. Possibly, the form at the time of processing may be any form such as fiber, thread, whole, cheese, woven fabric, non-woven fabric, or final textile products such as clothing and bedding products.

〔Example〕

Next, the present invention will be explained in more detail using synthesis examples and examples, but the present invention is not necessarily limited to the following examples.

Synthesis Example To a 500 d round bottom flask equipped with a high efficiency stirrer and heater are added 10 Of methyl glyoxylate methyl hemiacetal and 16 Of phosphorus pentoxide. The contents of the flask were heated to 100 DEG C. for 1 hour with stirring and then allowed to cool to room temperature.The resulting aldehyde ester was recovered from the residual phosphorus pentoxide by distillation.

To a 50 sl round bottom reaction flask equipped with a magnetic stirrer was then added 1ot (0.11 amol) of the freshly distilled aldehyde ester and 4-methylene chloride. The temperature of the flask and contents was lowered to about 0° C. and 0.5-0.05 M sodium diethyl methyl malonate was added to initiate polymerization. Keep the flask in a water bath until the temperature returns to 0-2°C (approximately 45°C).
Min) 0.18 m trifluoroacetic acid (I, 5 mol %) and H) s, s-ethyl vinyl ether were added to the mixture. The mixture was stirred at room temperature overnight. Approximately 2u of IM NaOH solution was added to the mixture and the volatile components were removed under vacuum.
The mixture with the addition of NaOH was stirred at about 0° C. for about 5 hours and then heated to about 40° C. for about 24 hours. Methanol and residual solvent were removed by rotary evaporation. The solution was concentrated to about 15%, precipitated in about 100 d of methanol and stirred for 30 minutes. The precipitate was collected in F and dried. The precipitate was then redissolved in distilled water, precipitated into methanol, stirred and collected. Yield is approximately 74.8%
Met. Analysis of the product, including chain length, by proton magnetic resonance (PMR) spectroscopy reveals that the product is predominantly a polymer of formula 1, where n is on average 40, with a small amount of It was shown that it is a mixture containing a polymer represented by the formula % formula %.

Comparative synthesis example Stirring rod, cooling tube, thermometer, N2 gas introduction tube, and dropping funnel were set 2! - 67 liters of ion-exchanged water in a 4-hole flask
0f was charged and the temperature was raised to 100°C. Inside the system is 100℃
80% acrylic acid 560t, 413%
492 tons of caustic acid solution, 150% ammonium persulfate, 741.5% hydrogen peroxide solution, and 132.8 tons were simultaneously added dropwise over 4 hours. The added layer was aged at 100° C. for 1 hour to obtain a fiber processability improver made of sodium polyacrylate. The molecular weight was approximately 5000 when measured by GPO.

Example 1 A polyester georgette fabric was dyed and then subjected to reduction washing to examine its level dyeing properties, reduction washing properties, and dye dispersibility of the dye liquor. The results are shown in Table 1. Dyeing conditions> Hardness of water used: 30'DH (same as above) Repenol v-saa (leveling dye manufactured by Kao Soap ■) 0.5
T/Z chemicals used Table 1 pH 4,5 (using acetic acid) Bath ratio 1:20 Temperature 130°C Time 40 minutes Reduction cleaning conditions> Caustic soda 1f/! Sodium hydrosulfide 22/J bath
Ratio 1:30 temperature
degree at 80℃
Evaluation after 10 minutes> Partial dark color unevenness was visually judged as a measure of level staining. In addition, reduction washability was measured by measuring the friction dyeing fastness and alkali sweat dyeing fastness of the cloth after reduction washing. All color fastness measurements were performed using the JIS method. Furthermore, water, dye (O
Range 0.1%, Blue O, 05%, Red
O, 05% concentration mixture), Levenol V-500 (0
, 02%) and the concomitant drug (0.2%) were prepared, and after being left for 24 hours, it was filtered using 5AP paper manufactured by Toyo F Paper Co., Ltd., and the state of the filtration residue was visually judged to determine the dye. 0 used as a measure of dispersibility Example 2 A nylon tropical fabric was dyed, and the dyeability and dispersibility of the dye were investigated. The results are shown in Table 2.

Dyeing conditions〉 Hardness of water used: 40° DH (acid dye manufactured by Nippon Kayaku ■) Repenol WA (leveling agent manufactured by Kao Soap ■) 1 t
/i Chemical used See Table 2 PH 4.0 (ammonium acetate used) Bath ratio 1:20 Temperature 100°C Time 40 minutes Notes Polypropylene tropical fabric was poured into the same bath during O dyeing.

After O dyeing, wash and vinegar in the usual way. Acid treatment was performed.

Evaluation> Partial dark color unevenness was determined with the naked eye as a measure of level staining, and the state of contamination of polypropylene was determined with the naked eye as a measure of polypropylene stain resistance. Also,
The washability was measured by measuring the friction dyeing fastness and alkali sweat dyeing fastness of the dyed fabric. The color fastness was measured by the J method 8 method. Furthermore, the dye dispersibility of 30 cc of the dye liquor was determined in the same manner as in Example 1.

Example 3 A cotton twill fabric was dyed and its hue, level dyeing property, and dye dispersibility of the dye solution were examined. The results are shown in Table 3.

Dyeing conditions〉 Hardness of water used 20°DH Glauber's salt 10% OWF Chemicals used Table 3 Reference bath Ratio 1:30 Dyeing temperature 90℃ Dyeing time 50 minutes Notes After dyeing, shiso-ping (evaluation) by the usual method Dyeing The color of the fabric was measured using an SM color computer model 5M-3 manufactured by Suga Test Instruments Co., Ltd., and the Hue value (value on the Munsell hue scale) was determined, which was used as a measure of hue. Also,
The uniformity of staining was determined by measuring the unevenness of partial dark color with the naked eye. Furthermore, dye dispersibility was determined in the same manner as in Example 1 for a mixed solution (staining solution) of water, dye (0.1%), and concomitant chemicals (0.1%).

Table 3 (Note) When the Hue value is FB, it indicates a blue-purple hue.The smaller the value, the closer the blue-purple is to B (Blue), and the larger the value, the closer it is to P (Putple, purple). It means blue-purple.

Example 4 Table 4 shows the results of dyeing a cotton knit and examining its hue, level dyeing property, and dye dispersibility of the dye solution.

Dyeing conditions> Hardness of water used: O and 20°DH Dye: Sumifix Red 3B, 1%
Owf (metal-containing type reactive dye made by Sumima Kagaku Kogyo ■) Glauber's salt sat/i Soda ash 15t/no Chemicals used Table 4 Reference bath Ratio 1:30 Dyeing temperature 60℃ Dyeing time 30 minutes Notes After dyeing, dye using the usual method - Evaluation of dye dispersibility The dye dispersibility was evaluated in the same manner as in Example 3 except that the concomitant chemicals were 0.2%.As is clear from the results in Table 4, water hardness was If the water hardness is higher than when it is low, there will be no deviation in Hue value and no discoloration (deviation from the hue that should be obtained from the dye used) unless a concomitant agent is used, but the leveling property and dye There is a problem with dispersibility. When the concomitant agent is ethylenediaminetetraacetic acid, problems occur such as deviation in Hue value and discoloration, and level dyeing properties and dye dispersibility are also slightly inferior. In contrast, when the fiber processability improver of the present invention is used as a concomitant agent, there is no deviation in Hue value, no discoloration, and good level dyeing and dye dispersibility. Note that when water hardness is low, if ethylenediaminetetraacetic acid is used as a concomitant agent, the Hue value will shift, resulting in a very large color change, resulting in a hue that is completely different from the hue that should be obtained from the dye used.

Example 5 A cotton twill fabric was dyed and its color density was examined. The results are shown in Table 5.

Dyeing conditions> Hardness of water used 0.25°DH Dye Mikathren Blue R day 111i1/f, '1% owf (Mitsui Toatsu Chemical Co., Ltd. thren dye) Sodium hydrosulfide 4 t/
J Kasei Soda 5t/! Concomitant chemicals See Table 5 Dyeing temperature 60°C Dyeing time 20 minutes Notes After dyeing, oxidation and soaping using a conventional method <Evaluation> Color measurement of the dyed cloth using SM Color Computer 5M-3 manufactured by Suga Test Instruments Co., Ltd. Then, the C value was determined and used as a measure of color density.

As is clear from the results in Table 5, when no concomitant chemicals were used, the C value decreased as the water hardness increased, resulting in no color density. When using concomitant drugs such as ethylenediaminetetraacetic acid,
Although there has been some improvement, the effect is small. On the other hand, when the fiber processability improver of the present invention is used as a concomitant agent, a deep coloring effect is exhibited in which the C value increases as the water hardness increases. This was the same even when the products obtained in Comparative Synthesis Examples were used.

Example 6 Desized cotton cabazine was scoured and its scourability was examined. The results are shown in Table 6.

<Scouring conditions> Hardness of water used: 20°DH Bath ratio: 1:25 Temperature: 95°C Time: 90 minutes Chemicals used: Refer to Table 6. Evaluation> A sample with a width of 2.5 cm was taken from the treated cloth, and the bisic method was applied. The height of water absorption for 30 seconds was measured as a measure of wettability.

Example 7 A desized polyester/cotton IS5/35 boblin was scoured by a pad steam method, and its scourability was examined. The results are shown in Table 7.

Refining conditions Pad□Hardness of water used: 15°DH Aperture □ Aperture '4 80% ■ Steaming - 105℃ x 60 minutes Wash with hot water □60℃×10 minutes ■ Wash with water □ Room temperature x 5 minutes Reviews This was carried out in the same manner as in Example 6.

As is clear from the results in Table 7, those using only caustic soda and a surfactant (Scorol F c -3oo) had a low water absorption height, lacked wettability, and had poor scouring properties. Even when acid or sodium tripolyphosphate is used in combination, the scouring property has not been significantly improved. On the other hand, those using the fiber processability improver according to the present invention have high water absorption, excellent wettability, and good scouring properties.Example 8 Obermeyer No. 940 twin yarn The knitting yarn was refined and its refinability was investigated. The results are shown in Table 8. Scouring conditions> Hardness of water used: 20° DH Bath ratio: 1:10 Temperature: 100°C Time: 2 hours Chemicals used: Refer to Table 8. Evaluation: Using the treated yarn, double knit knitting was performed. A vessel was prepared in the same manner as in Example 6.

As is clear from the results in Table 8, those using only caustic soda and a surfactant (Scorol c-11o) had low water absorption, poor wettability, and poor scouring properties. Even when sodium tripolyphosphate was used in combination, the scouring property was not significantly improved. On the other hand, one in which the fiber processability improver according to the present invention was used in combination had high water absorption, excellent wettability, and good scouring properties.

Example 9 Desized cotton sateen was simultaneously scoured and bleached to examine its performance. The results are shown in Table 9.

Scouring/bleaching conditions> Hardness of water used: 25°DH Bath Ratio 1:25 Temperature: 95℃ Time: 60 minutes Drugs used: See Table 9 Reviews This was carried out in the same manner as in Example 6.

As is clear from the results in Table 9, those using only caustic soda, surfactant (Scorol FO-300), hydrogen peroxide, and sodium metasilicate had low water absorption, lacked wettability, and had poor scouring properties. However, the combination of ethylenediaminetetraacetic acid or sodium tripolyphosphate has not significantly improved the scouring property.

On the other hand, those in which the fiber processability improver according to the present invention was used in combination had high water absorption, excellent wettability, and good scouring properties.

Example 10 A refined cotton Tenkasa knit was bleached and its bleaching properties were investigated. The results are shown in Table 10.

Bleaching conditions> Hardness of water used: 20°DH Bath ratio: 1:25 Temperature: 80°C Time: 30 minutes Chemicals used: See Table 10 <Evaluation> The texture of the treated fabric was evaluated using a sensory test method. For white discoloration, use SM Color Computer 8M manufactured by Suga Test Instruments Co., Ltd.
The color is measured using the Lab-based white variation formula (%). However, L = Measured lightness a = Measured fromerial roughness index b = White according to the measured fromerial roughness index The change (W) was determined and evaluated. The sewing property is 4
Evaluation was made based on the number of places where the base thread broke when the sheets were stacked and blank stitched at 3 oas using a lockstitch sewing machine with a +118 needle.

As is clear from the results in Table 10, the fabric made only with hydrogen peroxide, caustic soda, and No. 3 sodium silicate had a hard texture and white discoloration, and the stitching properties were poor, making it difficult to sew. No major improvements in bleaching properties have been made. On the other hand, fabrics in which the fiber processability improver according to the present invention was used in combination had a soft feel, excellent whitening and sewing properties, and exhibited good bleaching properties. In addition, although the comparative synthesis example has a soft feel and good whitening and sewing properties, it does not reach the level of the processability improver of the present invention.

Example 11 Raw silk was subjected to silk kneading treatment and its performance was investigated. The results are shown in Table 11.

Silk kneading conditions〉 Hardness of water used 20°DH Bath ratio 1:30 Temperature Boiling time 1 hour Chemicals used as shown in Table 11 Evaluation〉 The texture and gloss of the treated yarn were evaluated using a sensory test method. judge,
In addition, the unevenness of kneading was evaluated by observation of scanning electron micrographs.

As is clear from the results in Table 11, the Marcel soap and the soap containing only K of sodium silicate were inferior in texture, gloss, and uneven kneading. When ethylenediaminetetraacetic acid and sodium tripo-IJ 17phosphate are used together, an improvement is seen, but the effects of each are small.

On the other hand, when the fiber processability improver according to the present invention was used in combination, the texture, gloss, and lack of uneven stitching were all good, and an excellent silk kneading effect was obtained.

Example 12 A woven fabric using polyester spun yarn to which acrylic acid-based weaving paste was adhered was scoured, and its scouring properties were examined. Table 1 shows the results.
Shown in 2.

<Scouring conditions> Hardness of water used: 20° DH bath ratio: 1:25 Temperature: 95°C Time: 30 minutes Chemicals used: Table 12 shows <Evaluation> For the treated cloth, KIC8- manufactured by Kato Iron Works Co., Ltd. 1
A shear test was conducted using a shear tester, and a shear characteristic value of 2 HG 5 was determined. This value indicates that the smaller the value, the softer the texture. In addition, the treated cloth was dyed under the following conditions, and the dyeing unevenness of the obtained dyed cloth was observed (K) as a measure of the level dyeing property.

Staining conditions O-Levenol T D-5260, 2f/I.

(Dyeing aid made by Kao Soap ■ ON) H: 4.50 Bath ratio: 1:200 Temperature: 130°C 0 hours: 30 minutes As is clear from the results in Table 12, the product was made using only surfactant and caustic soda. The value of 2111G5 is large, the texture is hard and the texture is uneven, and the scouring property is poor. When ethylenediaminetetraacetic acid and sodium tripolyphosphate were used together, although each was slightly improved, no significant effect was observed. On the other hand, when the fiber processability improver according to the present invention was used, the value of 2HG5 was reduced, the texture was 7 tones, uneven dyeing was eliminated, and good scouring properties were exhibited.

Example 15 Refined polyester georgette was subjected to alkali reduction and its performance was investigated. The results are shown in Table 13.

<Alkali treatment conditions> Hardness of water used: 20" DH Bath Ratio: 1:50 Temperature: 90°C Time: 30 minutes Chemicals used: As shown in Table 13 Evaluation> The same method as in Example 12 was used to determine the scale of texture. Naru2iI
G5 was measured to evaluate the alkali weight loss property.

As is clear from the results in Table 13, the product using only caustic soda has a large 2H()5 and has an unfavorable texture.
Poor alkali weight loss properties.

When ethylenediaminetetraacetic acid and sodium tripolyphosphate were used in combination, the 2HG5 value was slightly smaller, but the effect was small. In contrast, when the fiber processability improver according to the present invention was used in combination, 2
HG5 is small, the texture is soft, and it has good alkali weight loss properties.

Example 14 Reactive dye KayaciOn Red E-83B 5
%Owf, 60 t/IJ of Glauber's salt, 20 parts of soda ash, 1:20 bath ratio, and 1 volume of various soaping agents shown in Table 141C for cotton knitted cloth dyed at 80°C for 60 minutes! ,
Soaping was carried out for 10 minutes at a bath ratio of 1:40 and a temperature of 95°C. After washing with running water at 40°C for 5 minutes after soaking, wash at 80°C.
It was dried in a dryer and measured for hot water staining, rubbing fastness, washing fastness, and alkali sweat fastness. The results are shown in Table 14.

Rubbing fastness is determined by the method of T Engineering S LO849, washing fastness is determined by the method of J Engineering S LO8[34, and alkali sweat fastness is determined by the method of J Engineering S LO849.
The investigation was conducted based on the method of Engineering 5LO88B. Judgment was made using the staining gray scale (Japanese Standards Association Dyeing Fastness Committee Meeting).0 The hot water staining level was determined using the staining gray scale (Japanese Standards Association Dyeing Fastness Committee Meeting) for stains on white cloth treated in the same bath as the dyed fabric. The degree of contamination of hot water was measured.

Claims (1)

[Claims] 1 General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Y is one or more comonomers randomly distributed in the polymer. n is on average at least 4, p is from 0 to about 2, and q is at least 1;
R_1 and R_2 are each any chemically stable group that stabilizes the polymer against rapid depolymerization in alkaline solutions, and M is an alkali metal, ammonium, 1 to about 4 carbon atoms. and alkanolamine groups having from 1 to about 4 carbon atoms in the alkyl chain). The fiber processability improver according to claim 1, wherein 2n is on average about 10 to about 200. 3. The fiber processability improver according to claim 1, wherein n is about 50 to about 100 on average. 4. The fiber processability improver according to claim 1, wherein p is 0. 5. The fiber processability improver according to claim 1, wherein p and q are each about 1. 6. The fiber processability improver of claim 1, wherein p is 1 and q is at least about 5. 7. The fiber processability improver according to claim 1, wherein R_1 and R_2 are each selected from the group consisting of alkyl, oxygen-containing alkyl groups, and oxygen-containing cyclic alkyl groups. 8 Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_
2CH_2O-, -CH_2CH(CH_3)O-, and combinations thereof, where R_3 is hydrogen or alkyl containing from 1 to about 20 carbon atoms, and M is sodium or potassium. A fiber processability improver according to claim 5. 9 R_1 is HO(CH_2CH_2O)-_1_-_
3, and R_2 is -(CH_2CH_2-O)-_1
The fiber processability improver according to claim 4, wherein n is _-_3H and n is about 10 to about 200 on average. The fiber processability improver according to claim 4, wherein 10 M is an alkali metal. 11 M is sodium, R_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n The fiber processability improver according to claim 4, wherein the fiber processability improver has an average of about 40.